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Thermodynamics

Basic Concepts
Introduction:
Thermodynamics deals with heat inter-action and work inter-action with the
substances called systems. Work and heat are forms of energy. Transfer of heat or work
to a substance brings about certain changes in the substance and whatever change
happens is called a process. Thermo means heat. Since work is also a form of energy,
thermo is taken to mean heat and work. Dynamics refers to the changes that occur as a
result of heat or work transfer.
Biological systems are capable doing work. For example, micro-organism is
capable swimming in the body fluid of its host. It needs to do the work. Where does
energy for doing this work come from? It is the metabolic activity that converts some
form of energy (Nutrition that it takes form host is a form of chemical energy) into work.
It is important then to understand how this happens so that we can exploit this to our
engineering benefit.
In thermodynamics we have work transfer, heat transfer and then we have a
system for interaction which undergoes a process. Let us look at these basic terms.

System:
We need to fix our focus of attention in order to understand heat and work
interaction. The body or assemblage or the space on which our attention is focused is
called system. The system may be having real or imaginary boundaries across which the
interaction occurs. The boundary may be rigid and sometimes take different shapes at
different times. If the system has imaginary boundary then we must properly formulate
the idea of system in our mind.

Surroundings:

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Every thing else apart from system constitutes surroundings. The idea of
surroundings gets formulated the moment we define system. System and surroundings
together form what is known as universe.

Closed system:
If the system has a boundary through which mass or material cannot be
transferred, but only energy can be transferred is called closed system. In an actual
system, there may not be energy transfer. What is essential for the system to be closed is
the inability of the boundary to transfer mass only.

Open system:
If the system has a boundary through which both energy and mass can transfer, then it is
called open system.

Properties:
Variables such as pressure, temperature, volume and mass are properties. A system will
have a single set of all these values.

Intensive properties:
The properties that are independent of amount contained in the system are called
extensive properties. For example, take temperature. We can have a substance with
varying amount but still same temperature. Density is another example of intensive
property because density of water is same no matter how much is the water. Other
intensive properties are pressure, viscosity, surface tension.

Extensive properties:
The properties that depend upon amount contained in the system are called extensive
properties. Mass depends upon how much substance a system has in it therefore mass is
an extensive property.

State:
It is defined as condition of a system in which there are one set of values for all its
properties. The properties that define the state of a system are called state variables.
There is certain minimum number of intensive properties that requires to be specified in
order to define the state of a system and this number is uniquely related to the kind of
system. This relation is phase rule which we shall discuss little later.

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Process:
The changes that occur in the system in moving the system from one state to the other is
called a process. During a process the values of some or all state variables change. The
process may be accompanied by heat or work interaction with the system.

Heat:
It is a form of energy that exists only in transit. This transit occurs between two points
which differ in temperature. Since it exists only in transit, it should be accompanied by
changes that occur in the system. The moment this energy cease to move, it appears as
internal energy. We shall discuss internal energy when we deal with I law of
thermodynamics.

Work:
It is also a form energy that exists only in transit. The work cannot be stored. Work is
defined as the product of force and distance through the force moves. Mathematically,


W f d


f d cos

where f is the force and d the displacement. Work is a scalar quantity.


Let us look at the following piston and cylinder arrangement containing some gas. The
system considered is the gas in the cylinder. It is exerting some pressure on the piston in
the upward direction. This is balanced by the atmospheric pressure plus the weight and

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therefore piston though it is free to move, does not move. If the weight is increased, then

dL
the piston moves downwards. The pressure of the gas increases and the movement of the
piston stops when the pressures become equal. The additional weight is doing the work
on the gas. The additional weight has to push the force created by the gas inside to move
the piston. So there is force and distance. But as the piston moves, the pressure
continuously changes. Therefore consider small distance (dL) for which work done (dW)
is also small as shown in the figure which results in small volume change (dV). Then by
definition of work, we have, if A is the cross sectional area of the piston

dW f dL
V
pA d
A
pdV

Integrating between the two locations of the piston,


2

W1 2 pdV
1

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This is the equation we use to determine the work. Please note that in general p cannot
be taken out of the integral sign as p may be continuously changing as above.

b
V

If we have a p vs. V curve, we can determine the integral as area under the curve.
The area under the curve a21b is the work done on the gas.
We can carry out a process differently with the same initial and final states given
by the points 1 and 2. Since it is a different process, the curve will be different. In that
case the area under the curve will also be different which means to say the work done is
different though the initial and final states are same. Thus the work depends upon the
process or path or how the state is changing. Such quantities are called path functions.
Since heat is also energy in transit as the work is, heat must also be a path function. No
matter what process, as long we have same initial and final states, it brings about the
same pressure difference. Such properties which depend only on state are called state
properties.

Equilibrium state:
A system is said to be in thermodynamic equilibrium if it satisfies the condition for
thermal equilibrium, mechanical equilibrium and also chemical equilibrium. If it is in
equilibrium, there are no changes occurring or there is no process taking place.

Thermal equilibrium:
There should not be any temperature difference between different regions or locations
within the system. If there are, then there is no way a process of heat transfer does not

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take place. Uniformity of temperature throughout the system is the requirement for a
system to be in thermal equilibrium.

Surroundings and the system may be at different temperatures and still system may be in
thermal equilibrium.

Mechanical equilibrium:
There should not be any pressure difference between different regions or locations within
the system. If there are, then there is no way a process of work transfer does not take
place. Uniformity of pressure throughout the system is the requirement for a system to be
in mechanical equilibrium.
Surroundings and the system may be at pressures and still system may be in mechanical
equilibrium.

Chemical equilibrium:
There should not be any chemical reaction taking place anywhere in the system, then it is
said to be in chemical equilibrium. Uniformity of chemical potential throughout the
system is the requirement for a system to be in chemical equilibrium.
Surroundings and the system may have different chemical potential and still system may
be in chemical equilibrium.

Thermodynamic process:
A system in thermodynamic equilibrium is disturbed by imposing some driving force; it
undergoes changes to attain a state of new equilibrium. Whatever is happening to the
system between these two equilibrium state is called a process. It may be represented by a
path which is the locus all the states in between on a p-V diagram as shown in the figure
below.

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1
p

2
V

For a system of gas in piston and cylinder arrangement which is in equilibrium, altering
pressure on the piston may be driving force which triggers a process shown above in
which the volume decreases and pressure increases. This happens until the increasing
pressure of the gas equalizes that of the surroundings. If we locate the values of all
intermediate states, we get the path on a p-V diagram.

Phase rule:
The two gas samples below have the same density, viscosity and all other intensive
properties.
1 m3 of nitrogen at a pressure of 2 atmosphere and 300 K
2 m3 of nitrogen at a pressure of 2 atmosphere and 300 K
If a gas behaves ideally, then

pV nRT
n
p

V RT
If M is the molecular weight of the gas, then
m nM pM

V
V
RT

pM
RT
Thus the density of an ideal gas depends upon only temperature and pressure as all other

quantities are constants. Since p and T are same for the above nitrogen samples, density is

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same. If we take out 1 cc of sample from any of those two, by observing only this 1 cc
sample we can never from where we took the sample. This means to say the samples are
exactly same and indistinguishable. They are said to be in the same state.
In order to define this state of nitrogen, we need only T and p. Thus we need minimum
two variables to specify the state. This number is given by Gibbs phase rule which is
given by

F 2 N

where
F

: degrees of freedom

: Number of phases

: Number of components

For the above example, number of phases is one; number of components is one therefore
the degrees of freedom are two. For a system containing liquid water and its vapor in
equilibrium, we get the degrees of freedom to be one.

Following is the phase diagram of water which describes in what phase or phases
it can exist for different temperature and temperature.

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Liquid
p

Solid
Vapor
T
For the system to have two phases, if we mention the temperature alone given by

the vertical line, the pressure has to be the one given by horizontal line. Given the
pressure, its temperature gets fixed. Thus we have a freedom of fixing only one of them
which amounts to say degrees of freedom is one.

Heat reservoirs:
If the temperature of the system does not change if we remove a finite quantity of heat
from it, then the system is said to be heat reservoir. If the temperature of the system does
not change if we add a finite quantity of heat to it, then the system is said to be heat sink.
Ocean can be made to act either as heat reservoir or heat sink.

Heat Engine:

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Work and heat are forms of energy and are inter-convertible. Any device which converts
continuous supply of heat into useful work continuously is called heat engine. For any
system to undergo continuous process, it should be cyclic. The detailed mathematical
treatment of heat engines will follow in 5th chapter on second law of thermodynamics.

Irreversible process:
If a thermodynamic process takes place in such a way that we can retrace the path
exactly, the process is called reversible. Consider a piston and cylinder arrangement with
piston free to move at some pressure and temperature in equilibrium. The pressure of the
gas is balanced by a pressure equal to sum of atmospheric pressure and the weight on the
piston pan as shown. If the weight on the piston is reduced, then the piston moves up. Let
us just displace the part of the weight horizontally. This involves work. The piston moves
up as it is free to move until the pressures again become equal.

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State -2

State -1

Following is the p-V diagram for the process.

2
p

V
Looking at the sequencing of the events, it is

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1.

Removal of part of weight on the piston which takes some work.

2.

Moving of piston upward following some path on p-V diagram as shown.


Reaching a new steady position called state 2.

Reversal of these events will mean


1.

Piston moving downward from state-2 to state-1.

2.

Weight moving on to the piston.

Can this reversal be possible? During expansion step, the system does work on the
surroundings. In reverse then, the surroundings should do the work at state 2. This is
not possible as the system and the surroundings have the same pressure. Exact reversing
is not possible. The process of bringing the weight on the piston pan is also not possible
as we need to do only by moving horizontally. The pan level is higher than that of the
weight. This requires extra work to be done. Further, in moving the weight work was
done on the weight. In reverse then, the weight should do the work, go and sit on the pan!
Clearly this is ridiculous which is not possible.

In order for a process to be reversible, the driving force must be infinitesimally small. If
we remove the weight bit by bit and place it horizontally, every bit would be placed one
above the other and then piston moves upward. At any point, the piston and the bit
removed are at the same level. As a result, at any point, we can move the bit horizontally,
making the piston move a bit down where the next bit of weight is available at the same
level. Reversing is thus possible.

However there is one work that can never be reversed even in this process. That is the
work done on the bit to move it horizontally. But this is less irreversible compared to the
earlier process where large part of the weight was removed. Look at the state-2, in order
to reverse; the weight has to be lifted by some vertical distance which is missing in the bit
by bit process. We can only strive to make a process only closer to reversibility.

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First law is a statement of law of conservation of energy. For a closed system, since there
is no mass exchange with the surroundings, the total energy of the system must be always
a constant. One form of energy may be converted into another. The system may possess
several forms of energy such as kinetic energy, potential energy, internal energy.

Potential energy:
It is the energy possessed by a body by virtue of its position. An object kept at a height z,
possesses energy to do the work. A spring kept in a compressed state is also capable of
doing work. A body is said to be possessing energy only if it can lift weight by some
mechanical means. If we tie a rope to a body at higher level, pass the rope over a pulley
and tie the other end to another body whose mass is slightly lower, the second body will
be lifted. To one end of the compressed spring in the vertical position, tie a weight and
then release the spring. The weight goes up. Thus a body at higher level or spring in its
compressed state possesses energy. The potential energy of a body of mass m at height of
z from some arbitrary level (reference level) is given by

EP mgz
Arbitrary level may by any level. As long as the same, the changes in energy will also be
same. The changes in potential energy as the level changes will be
EP mg( z f zi ) mgz

Kinetic energy:
It is defined as the energy possessed by a body by virtue of its velocity. For a body of
mass m which is moving with a velocity u, the kinetic energy is given by,

EK

1 2
mu
2

Change in kinetic energy is

1
1
2
2
EK m(u f ui ) mu 2
2
2

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Internal energy:
When some external work is transferred to a body, its temperature increases indicating
rise in internal energy. Internal energy is due to molecular energy of vibration and
rotation.

First law of thermodynamics for a closed system:


If Q is the amount of heat transfer to a system which does W amount of work (work
transfer form the system), then the change in the total energy of the system will be Q
W. This change will have its implications on the kinetic, potential and internal energy.
Since law of conservation is to be valid, the change in internal energy Q W must be
equal to the changes occurring in all forms energy. Mathematically,

Q W U EP EK
Generally, the changes in kinetic and potential energy will be negligible compared to heat
and work interaction,

Q W U
This is first law of thermodynamics. Note that Q is the heat transfer to the system and W
is work done by the system.

Cyclic process:
If the process occurs in such a way that periodically its state repeats then the process is
called cyclic process. The following p V diagram represents a cyclic process.

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p
1
2

The states 1, 2 and 3 keep repeating in the process in that order. Not only this, all the
states in between also will repeat. Every time process state changes from 1 to 2, 2 to 3
and 3 to 1 following the same paths. During such processes, there will be heat and work
interaction. All the properties will get the same values at state 1 regardless of number of
times cycle repeats. Thus

U1 2 31 V1 2 31 p1 2 31 T1 2 31 0

First law applied to a cyclic process:


Since the change in internal energy is zero,

U Q W
Q W 0
Q W
This means that net heat transfer to the system is the net work done by the system.
Cyclic process consists of several steps. In the cyclic process shown in the diagram, there
are three steps viz., 1-2, 2-3 and 3-1.

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Let us have another cyclic process for which heat and work interaction are known as
below.

Step

Heat interaction

Work interaction

1-2

Q1-2 is added to the system

No work interaction

2-3

Q2-3 is removed form the system

W2-3 is the work done by the system

3-1

Q3-1 is added to the system

W3-1 is the work done on the system

Net heat transfer to the system, Q Q1 2 Q2 3 Q31


Net work done by the system, W W2 3 W31 and Q W

Flow processes:
So far we considered closed systems only. Let us look at open systems. Mass exchange
can occur. If the process variables do not change with respect to time for the system, the
process is said to be under steady state conditions. Under such conditions the mass of the
system is constant. This is due to the equality of mass entering and leaving.

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If the system as a whole is moving undergoing changes, it constitutes steady state flow
process only when the system at a fixed location will have fixed values.

Heat in, Q
z1
2

z2

Work output, Ws

This diagram shows an open and steady state flow process. The equipment considered is
between 1 and 2. The gas enters at 1 and leaves at 2. Steady state flow process requires
mass entering at 1 is equal to mass leaving at 2. If certain mass of gas considered to be
the system, such as cylindrical shaped gas at 1, when it reaches a particular location such
as A, it will be at a state (having certain fixed values for all the properties). No matter
what time, the system at A will be in the same state. This is true for all locations.
However, state of the system differs from location to location. There is no variation of the
state with respect to time at a given location.

First law applied to flow process:


Following is the equipment through which the steam is flowing.

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Heat in, Q
z1
2

z2
Work output, Ws

Steam enters at 1 and leaves at 2. There is a heat exchanger which adds heat Q to the
steam making it superheated. The superheated steam runs the turbine and shaft work is
obtained. Thus the gas does the work Ws. The kinetic, potential and internal energy of the
gas changes as it goes from one location to the other. The entrance 1 is at height z1 and
exit is at height z2 from some reference datum. The velocity of the gas varies as the flow
area varies along the path.
Let us consider unit mass of steam whose volume is the volume of cylinder shown at
location 1. This steam element enters the equipment, goes through it receiving heat Q in
the exchanger, doing work at the turbine and comes out at 2.

There are changes

occurring in potential (as the height at which the steam element is present changes),
kinetic energy (as the velocity changes) and internal energy. Let u1 and u2 be the
velocities at location 1 and 2. Change in kinetic energy, since m =1, is

E K

1 2
2
(u 2 u1 )
2

Change in potential energy of the steam from 1 to 2 is

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E P mg( z 2 z1 )
Let the change in internal energy be U . We must account for all heat and work
interaction that occur during the process of steam element moving form 1 to 2. The heat
Q is getting transferred in the heat exchanger to the steam element. Apart from work
output of the turbine, there are other fork forms. At location 1, the surrounding has to do
the work on the steam element to push it into the equipment. If the pressure of the steam
is p1, and the cross sectional area of the pipe is a1, then the distance moved by the steam
element is V1 / a1 where V1 is the specific volume of the steam at 1. The work done at the
entrance on the steam element at 1 is then,

W1 ( p1a1 )

V1
p1V1
a1

(Work done on the system)

Similarly work needs to be done by the steam element at section 2 as it has to push the
surrounding which is given by
W2 ( p2 a2 )

V2
p2V2
a2

(Work done by the system)

The entrance and exit work are also called as flow work. The product of pressure and
volume is the flow work.
If the steam element gets into the equipment, it receives work done by the previous steam
element and uses it to push the element next to it. Thus the net work is zero for all the
locations inside the equipment.
Thus the net work done by the element,

W WS W2 W1

W WS P2V2 P1V1
Substituting in first law of thermodynamics,

Q W E K E P U
Q (WS p 2V2 p1V1 ) E K E P
Q WS E K E P U 2 U 1 p 2V2 p1V1
Q WS E K E P (U 2 p 2V2 ) (U 1 p1V1 )

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The group U pV occurs frequently in flow processes and is called enthalpy denoted by
the letter H.
H U pV

Since internal energy, pressure and volume are state functions, enthalpy is also state
function. The above equation becomes,

Q WS E K E P H 2 H 1
Q WS E K E P H
This equation is first law of thermodynamics applied to flow processes. If the changes in
potential and kinetic energy are very small then,

Q WS H

Heat capacity:
Heat capacity of a substance is defined as the heat transfer necessary to bring about a
change in the temperature of unit amount of substance by one degree centigrade. Since it
is heat transfer which is a path function, it depends upon the way heating is done. For
example gases can be heated to increase the temperature by two different methods. The
unit quantity of gas taken in container with rigid wall, when heated its volume remains
constant. Another method is to have the wall which is flexible. If the piston is movable in
the piston and cylinder arrangement, gas when heated pushes piston and pressure will be
constant. Even if we take unit amount of gas in both these heating methods, it is observed
the heat transfer is not the same. Thus we have heat capacity and constant volume and
heat capacity at constant pressure. Mathematically,

dQ
dT

Cp

dQ
dT

CV

dQ
dT V

The heat capacity at constant volume will not be equal to that at constant pressure.

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PVT Behavior of fluids


Pressure, temperature and volume of gases vary in a definite manner. Based upon the
conditions, matter can exist in solid, liquid and gas phase. This is represented in graphical
form as below. This diagram is for pure water. All pure substances will have more or less
similar diagrams.
p T diagram for pure water

Fluid
Critical Point.

Liquid

Solid
d
a

Gas

Vapor

T
Based upon the values of pressure and temperature, if the point lies in a region, the
substance will exist in the corresponding state represented. For example the point a
represents solid state and b represents vapor state. Any point lying on the curve
represents both the phases which are in equilibrium. For example, the point d represents
liquid water and its vapor in equilibrium. Thus there are numerous pair of pressure and
temperature values on the curve and all those points represent liquid and vapor in
equilibrium. Each curve will have always two phases in equilibrium.
The point where all the curves meet is called triple point and at this condition, all the
three phase exist in equilibrium. Critical point is the highest temperature and highest
pressure where the liquid and its vapor can exist in equilibrium.

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For all pressures and temperatures higher than those at critical point, the liquid and vapor
properties become similar. This state is called fluid.
Phase is considered liquid if it can be vaporized by reduction in pressure keeping T
constant. This is represented by vertical downward arrow in the figure. The initial point is
in liquid phase region. Phase is considered gas if it can be condensed by reduction in T
keeping p constant. This is shown by horizontal arrow pointing towards left. The point a
represents solid state which on increasing the temperature at constant pressure, only the
temperature of the solid increases until it reaches curve where first drop of liquid appears
and beyond this only vapor exists. This is shown as arrow a b.
The other way is representation using p V diagram for pure substance which is given in
the next figure.

S/L

fluid

pC
S

Gas

p
L/V

V
TC

S/V
VC

p V diagram for pure substance


There are regions where two phases co-exist in equilibrium. The dashed curve labeled Tc
represents an isotherm at critical temperature.

In thermodynamics, we deal largely with either vapor or gases. The significant portion of
the diagram is given below.

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p V diagram for pure substance

fluid
C

pC
L

Gas

p
3

4
V
TC
T1

L/V
VC

The substance at point 1 is in liquid state. If we decrease pressure keeping temperature


constant, the volume decreases along the dashed curve. But this change is very small and
this is why liquids are considered incompressible. Volume change with pressure at
constant temperature is negligible for liquids. Decreasing pressure from 1 at constant
temperature (T1), a point 2 will be reached where first bubble of vapor appears. Any
further attempt to decrease the pressure fails bringing pressure down, instead more and
more liquid becomes vapor and the pressure and temperature remain constant represented
by dashed horizontal line. Thus point such as 3 represent liquid and vapor in equilibrium.
Further attempt in decreasing the pressure brings the state to the point 4 where all the
liquid becomes vapor. Further decrease in pressure at constant will follow the dashed
curve in the gas region. Thus the dashed line represents an isotherm (T1). Given in the
figure there is one more isotherm at a temperature less than T1. The dumb bell shaped
curve represents the locus of all points on all isotherms where the points similar to 2 and
3 lie. The isotherms of higher temperature lie on higher and saturated liquid and vapor
volume become closer and closer and finally merge at the critical point. This is point
where liquid and vapor cannot be distinguished. Isotherm TC has a point of inflexion at
the critical point.

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A point on the curve is called point of inflexion if there is a tangent at that point which
lies on either side of the curve as shown below.

How do we represent this complicated behavior mathematically? This is a challenge


which led to lot of research and we have several mathematical equations. All these
equations do have limitations. We will use simple mathematical equation. This is not a
limitation as no matter what equation all it does is relate pressure, temperature and
volume of gases.

Ideal gas equation: For one mol of any gas,


pV RT
Internal energy is a function of temperature only.
T2

T2

U CV dT

H C P dT

T1

T1

No matter what process, the changes in internal energy and enthalpy are given by the
above expression not only for ideal gases even for real gases.
This law is valid for low pressures, large volumes and low temperatures.
At constant pressure

dQ
CP

dT p
dQ C P dT ,
At constant volume

dQ
CV

dT V
dQ CV dT ,
Isochoric Process:

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Any process in which volume of the system does not change is called isochoric process.
Work done is zero.

U Q W

U Q
T2

U CV dT CV (T2 T1 )
T1

T2

H C P dT C P (T2 T1 ) Q
T1

Isobaric process:
dU dQ pdV

dQ CP dT
dU C P dT pdV
C P (T2 T1 ) p(V2 V1 )

H Q C P (T2 T1 )
W p(V2 V1 )

Relation between heat capacities:


H U PV
H U RT
dH dU RdT

CP dT CV dT RdT
CP CV R
CP CV R

CP CV

Isothermal Process:
Since the temperature is constant there will not be any change in internal energy.

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dU dQ dW
dQ dW
Q W

V2

pdV

V1

V2

pdV

V1

V2

RT
dV
V
V1

p1
p2
p
RT ln 1
p2

RT ln

Q W RT ln

p1V1 p2V2

T1
T2

V2
p
RT ln 1
V1
p2

H U 0

Adiabatic Process:
There will not any heat exchange, Q = 0.
dU dW
RT
dV
V
RT
CV dT
dV
V
dT
R dV

T
CV V
CV dT

CP
R
1
CV
CV
CP
R
1
CV
CV

R
1
CV

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dT
dV
( 1)
T
V
dT
dV
( 1)
T
V
T2

2
dT
dV

1
)
T T
V V
1
1

ln

T2
V
( 1) ln 2
T1
V1

V
T
ln 2 ln 1
T1
V2
T2
T1

V
1
V2

The temperature and volume change according to the above equation.


The pressure, temperature and volume all vary in the adiabatic process.
Let us get a relation between the other variables.
Since the gas is ideal,

p1V1
pV
2 2
T1
T2
T2 p2V2

T1
p1V1
p2 V1 V1

p1 V2 V2

p1V1 p2V2

pV const
dU dW
T2

U W CV dT
T1

W CV (T2 T1 )

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R
(T2 T1 )
1

RT2 RT1
1

p2V2 p1V1
1

p1V1 p2V2

p1 V2

p2 V1

p1V1 p2 p1

W
1
1 p1 p2

V2 p1

V1 p2

p1V1
p2 p2

1 p1 p1

1
1

p1V1 p 2
W
1
1 p1

p1V1 p2
1
1 p1

1 /

p1V1 p2
1
1 p1

1 /

H C P dT
1
2

U CV dT
1

Polytropic Process:

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It is a representation of all the processes in a mathematical form as below.

pV n const
Sl. No

Process

1.

Isobaric

2.

Isothermal

3.

Isochoric

Generally n lies between 1 and .


.
Guidelines to represent processes on p V diagram:

p
T2
T1

V
In the figure above there are two isotherms shown. For these isotherms, T2 T1. There is
one isotherm passing through every point on p V diagram. Higher the temperature
higher will be location of the isotherm. As they go downwards they converge as shown.
No two isotherms will ever intersect.

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Similarly every point has an adiabatic curve passing through it. The adiabatic curve
follows the relation pV const . Thus every point is an intersection of an isotherm and
an adiabatic curve as shown below. The adiabatic curve is steeper.

Adiabatic curve
p
Isotherm
V
No two adiabatic curves will ever intersect.
The mathematical relation between pressure, volume and temperature applicable all
ranges of values has not been possible. However, there are equations which are valid over
certain ranges.

Conditions for any equation to be equation of state:


1.

The equation should reduce to

pV RT
As p 0.
2.

p-V curve should have a point of inflexion for isothermal at critical point C,
2 p
p

0 and 2 0
V C
V C

Van der Waals equation of state:


a

p 2 V b RT
V

Here a and b are constants that depend upon the gas. If we apply the partial derivative
conditions, we get,

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27 R 2TC
RT
;b C
64 pC
8 pC

The Van der Waals equation is cubic in V. Therefore it should have three roots for a
given set of values of pressure and temperature and for a given substance. For any
temperature higher than critical temperature, there is one positive root. For critical
temperature and critical pressure, all the three roots will be equal which gives critical
volume. For temperature and pressure less than critical values, there will be three roots,
least one gives the molar volume of saturated liquid and highest gives that of saturated
vapor which are volumes given by the two ends of horizontal section of the isotherm.

Redlich Kwong Equation:


p

RT
a

V b V (V b) T

Applying the partial derivative condition, we get


a

0.4278R 2TC
pC

5/ 2

;b

0.0867 RTC
pC

Note that the above equations reduce to the equation pV RT , as p 0.


Other equations of state are Peng Robinson and Virial equations.
Numerical problem:
Air is compressed from an initial state of 1 bar and 298 K to a final state of 5 bar and 298
K through two mechanically reversible processes in a closed system. First heating at
constant volume followed by cooling at constant pressure. Calculate W, Q, change in
enthalpy and internal energy. Use CP

7R
5R
, CV
.
2
2

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2
a
p
Isotherm at 298 K
1
V
The path is shown in the figure. 1 - a represents heating at constant volume and a - 2
represents cooling at constant pressure. Note that initial and final states lie on a single
isotherm.
Let us do the calculations for one mol of gas.
For the path 1 a, since volume is constant, work done is zero.

dU dQ
dU CV dT
Ta

U1 a CV dT
T1

To use this we need to know temperature at a. Since it is closed system and volume is
same at 1 and a,

paTa p1T1
Since pressure at a is same as that at 2,

Ta

p1T1 p1T1 5(298)

1490 K
pa
p2
1
Ta

U1 a CV dT
T1

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1490

5R
dT
2
298

5R
(1490 298)
2
5(8.314)

(1490 298)
2
24775.7 J
24.775kJ

Thus Q1-a = U1-a = 24.775 kJ.


1490

H1 a

C dT
P

298

7(8.314)
(1490 298) 34686 J 34.686kJ
2

You can use the formula

H1 a U1 a ( pV )1 a U1 a ( paVa p1V1 )
to calculate change in enthalpy.
For the step a 2,

dU dQ dW

T2

U a 2 CV dT
Ta
298

5R
dT
2
1490

5R
(298 1490)
2
24775.7 J
24.775kJ

298

H a 2

C dT
P

1490

7(8.314)
(298 1490) 34686 J 34.686kJ
2

dW pdV

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Wa 2 pdV
a

Along the path a 2, since pressure is constant and equal to 5 bar,


2

Wa 2 pdV
a

5x105 (V2 Va )

We should know the volume at a.


From gas law, at the initial condition, V1

8.314(198)
0.02477m3
5
1x10

Note that we have taken one mol.

p2V2 p1V1

T2
T1
The temperatures are equal,

V2

p1V1
p2

1(0.02477)
5
0.004954m3

Similarly,

Va

RTa 8.314(1498)

0.1245m3
pa
1x105

Wa 2 p(V2 Va ) 5x105 (0.004954 0.1245) 59773J 59.773kJ


Since the volume is decreasing, work is done on the system.

U a 2 Qa 2 Wa 2
24.775 Qa 2 (59.773)
Qa 2 84.548kJ
For the entire process,

Q1 2 Q1 a Qa 2 24.775 (84.548) 59.773kJ

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U1 2 U1 a U a 2 24.775 24.775 0
H1 2 H1 a H a 2 34.686 34.686 0

W1 2 W1 a Wa 2 0 (59.773) 59.773kJ
Since there are no changes in internal energy and enthalpy, work done on the system is
given out as heat.

Determination of changes in internal energy and enthalpy:


No matter what is the process the internal energy and enthalpy are determined using the
following formulae.

dU CV dT
dH CP dT
If the process is isochoric, then dU CV dT dQ.
If the process is isobaric, then dH CP dT dQ.
Let us recall that
1.
For ideal gases internal energy is a function of temperature only.
2.
The change in internal energy is a state function.
Let us take an adiabatic process and determine change in internal energy.

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2
p

1
V
Consider two states (1) and (2) on an adiabatic path. There is one isotherm for each state
as shown. Adiabatic curve at (1) is steeper than the isotherm. Whether the process
follows adiabatic path or another curve shown in the figure or any arbitrary path, as long
the initial and final state are same, we get the same change in internal energy.

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2
p

1
V
Let us replace adiabatic path by two steps
1.

1 a constant volume process followed by

2.

a 2 isothermal process

to accomplish the same change in the state.

U12 U1a U a 2

Since step 1 a is a constant volume process, dU CV dT will have to be used. The step
a 2 is isothermal and therefore dU = 0.
Ta

U12 CV dT 0
T1

Since Ta T2 ,

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T2

U12 CV dT
T1

Any process between any two states can be replaced by either an isothermal process
followed by constant volume process or constant volume process followed by an
isothermal process. The total change in internal energy is the change in internal energy
for constant volume step only. Thus no matter what process the change in internal energy
is given by dU CV dT .

Same idea may be extended to change in enthalpy.

Deviations of real gases form ideal behavior:


The deviation from ideal behavior is measured using what is known as

compressibility factor defined as the ratio of volume determined using ideal gas law
to the actual volume at any given temperature and pressure.

Vactual pV

Videal RT

For ideal gases, Z = 1. Higher the value Z away from one higher will be the non-ideality.
Following figure gives the value of Z as a function pressure for different gases. All gases
approach ideal gas behavior at low pressures. This figure is called compressibility chart.
There will be as many curves as there are number of gases. The chart that is given here is
for one temperature. Therefore this figure becomes highly cumbersome if applied for all
gases and all temperatures.

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N2

CH4

1.0
Z
C2H6
p
Theory of corresponding states:
It states that all fluids, when compared at the same reduced temperature and reduced
pressure, will have same compressibility factor and all deviate from ideal behavior to the
same extent.
The reduced pressure and temperature are defined by

pr
Tr

p
pC
T
TC

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Tr 1.5
Tr 2.5

Z
Tr 1.0

pr
Here all gases with the same reduced temperature and pressure lie on the same curve.
This chart is called generalized compressibility chart. Different gases are indicated by
different points on the curve. There will be as many curves as there are temperatures.
This is less cumbersome compared to compressibility chart.

N2
CH4

Tc

189.
3
286.0

83.7
5
114.

126.
2
190.

p
c

pr

33.
5
45.

r
1.
5
1.

2.
5
2.

The above table gives two gases with the same Z for different T and p. The reason is that
the critical values are different.

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Standard Heat of reaction:


It is defined as the enthalpy change accompanying a reaction when both reactants and
products are at their standard states at 298 K and is denoted by H 0 298 .

2C( s ) O2 ( g ) 2CO( g )

H 0 298 221.2 kJ

If the stoichiometry of the above reaction is represented as

C( s )

1
O2 ( g ) CO( g )
2

Then,

H 0 298

221.2 kJ
110.6 kJ
2

Standard Heat of Combustion:


The standard heat of combustion of a substance is defined as the enthalpy change
accompanying the reaction when one mol of the substance undergoes combustion when
both reactants and products are at 298K.

H 0 298 2336.24kJ

2CH 3 CHO( l ) 5O2 ( g ) 4CO2 ( g ) 4 H 2 O;


The heat of combustion is 1168.12 kJ.

The standard heat of formation:


Standard heat of formation of a substance is defined as the change in enthalpy
accompanying the formation of 1 mol of the substance from the constituent elements
when the reactants and products are at 298K.

2C( s ) O2 ( g ) 2CO( g )

H 0 298 221.2 kJ

Standard Heat of Formation of Carbon monoxide is H

110.6 kJ .

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Hesss Law of constant heat summation:


The net enthalpy involved in a reaction is the same whether the reaction takes place in a
single step or in a series of steps.

A B C

Let A and B react to form C with heat of reaction H. Let there be one more method of
carrying out this reaction in two steps as given below.

A B AB
AB C

H1
H 2

Treating arrow as an equal sign, adding these two reactions gives,

A B C ,
It has been found that

H1 H 2

H1 H 2 is same as H .

This idea is used to determine heat of reaction from heat of formation or heat of
combustion data.
For example if we want to determine heat of formation of sulfuric acid, we must
determine this from the reaction,

H 2 S 2O2 H 2 SO4
No matter what we do, the above reaction cannot be carried out. Let us carry out other
possible reactions such that the over-all reaction is the formation reaction as below.

S O2 SO2
2 SO2 O2 2 SO3

H1 ----------(1)
H 2 ----------(2)

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SO3 H 2 O H 2 SO4
H2

1
O2 H 2 O
2

H 3 -----------(3)
H 4 ----------(4)

2(1), 2(3) and 2(4) gives,

2 S 2O2 2 SO2
2 SO2 O2 2 SO3

2 H1 ----------(1)
H 2 ----------(2)

2 SO3 2 H 2 O 2 H 2 SO4
2 H 2 O2 2 H 2 O

2 H 3 -----------(3)

2 H 4 ----------(4)

Adding these equations along with heat of reactions,

2 H 2 2 S 4O2 2 H 2 SO4
and heat of this reaction will be 2( H1 H 3 H 4 ) H 2
Therefore heat of formation of sulfuric acid is H1 H 3 H 4

H 2
2

This is how Hesss law can be used to determine the heat of reaction of a reaction from
heat of reaction of other reactions.

First deals with law of conservation of energy and defines internal energy.
A stone falls decreasing its potential energy and converting it into kinetic energy. Just
before it strikes the ground, it has maximum kinetic energy. From there why does it not
go up decreasing its kinetic energy and converting it into potential energy?

If we keep two bodies at different temperature in contact, why there is no heat transfer
from a body of low temperature to a body at higher temperature?

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When we remove the wall which separates two gases, the two gases mix together without
any external work done on them. Why then the two gases in a mixed state separate
themselves without any external work?

For all the processes mentioned above there is absolutely no violation of I law. In spite of
that, we do not observe these processes. It appears that there is some sense of direction
for spontaneous processes. There is nothing in the first law to indicate any such direction
to any process.

Is there any difference between heat and work though they are both forms of energy? If
they inter-convertible, then any cyclic process should be able to convert all the heat
supplied into work completely as change in internal energy is zero. Does it happen? It has
been found that we cannot have a device whose sole effect is conversion of heat supplied
into work completely. Let us look at why this is so with an example of a process.

In the following figure, there is a heat exchanger where heat is supplied (Q1) to the
system which is water in this case and generates steam at high pressure. The steam flows
into a turbine and rotates it producing useful work WS. From the turbine, we get steam at
relatively lower pressure than with which it entered. The objective here is to convert heat
Q1 into work. Since this heat is available, can we send the steam from turbine directly
into the heat exchanger in order to make it work continuously so that we get continuous
supply of work? This is shown by a dotted arrow.

The moment we establish this connection, whole process comes to an abrupt stop! We
have lower pressure steam line going into the heat exchanger in which there is higher
pressure steam. If there is connection like this, why does steam preferentially go into the
turbine line? It will enter into both the lines and stop the turbine. Therefore, in order to
have this going on, we must condense the steam bring about a change in its state so that it
can be fed to the heat exchanger. This state must be same as that of feed water to the heat
exchanger.

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Turbine
WS

Heat Exchanger
Q1

Condenser

Q2

Thus there is no way Q2 = 0. We cannot device any process which converts Q1


completely into work. The work obtained Ws is less than Q1 by an amount equal to Q2.
By first law, since for a cycle change in internal energy is zero,

WS Q1 Q2
Practically Q2 cannot be zero.
If we analyze any cyclic process, there will be several heat and work interactions, such
that net work done is equal to net heat supplied. There will be always one step in which
there is heat removed which brings down the amount of heat that is getting converted into
work.

This fact is the basis of statement of II law of thermodynamics. There are several
statements for the II law which are equivalent. In fact we can deduce one from any other.
All the statements are given below.

Second law of thermodynamics:


1.

Heat cannot by itself pass from a cold to a hot body.

2.

All spontaneous processes are to some extent irreversible and are


accompanied by degradation of energy.

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3.

It is impossible to construct a heat engine that operates continuously in a cycle


to produce no effect other than

conversion of heat supplied completely into

work. This is called Kelvin Planck statement.


4.

It is impossible to construct a heat pump (reverse heat engine) that operates


continuously to produce no effect other than transfer of heat from low
temperature body to a high temperature body.

Carnot cycle and Carnot engine:


The Carnot cycle consists of four steps and all the four steps are reversible. The cycle is
shown in the diagram below.

TH
TC

B
D

There are two isotherms and two adiabatic processes as shown. The isotherms are at TH
and TC.
AB Reversible isothermal expansion
BC Reversible adiabatic expansion
CD Reversible isothermal compression
DA Reversible adiabatic compression
According to first law, it can be shown that

QAB WAB RTH ln

pA
pB

WBC CV ( TH TC )

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pC
pD

QCD WCD RTC ln


WDA CV ( TC TH )
The net work done is given by

Wnet WAB WBC WCD WDA

RTH ln

p
pA
CV ( TH TC ) RTC ln C CV ( TC TH )
pB
pD

For adiabatic process BC,

TH pB

TC pC

( 1 ) /

TC pD

TH pA

( 1 ) /

And for the adiabatic process DA,

From these two,

pD pA

pC pB
Net work done becomes,

Wnet R( TH TC ) ln

pA
pB

Heat supplied with an objective of converting into work is

QAB W AB RTH ln

pA
pB

The efficiency is defined as

Wnet

QAB

R( TH TC ) ln
RTH ln

pA
pB

pA
pB

TH TC
TH

It is clear that efficiency of Carnot engine depends upon only the temperatures between
which it is operating and not on the working substance undergoing the cycle. Since
Carnot engine is reversible, it must have maximum efficiency.

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From first law,

Wnet QAB QCD

Wnet QAB QCD


Q
T

1 CD 1 C
QAB
QAB
QAB
TH
1

QCD
T
1 C
QAB
TH
QCD TC

QAB TH

Let QCD is heat removed, and be equal to QC; and heat added as QH, with sign
convention,

QC TC
which can be simplified to

QH
TH

QH QC

0
TH TC
This equation is applicable to the complete cycle and any quantity that adds to zero for
the cycle is a state property. Thus Q/T is a state property called entropy. Thus second law
of thermodynamics brings in the idea of entropy.

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Efficiency of engines:
The efficiency of reversible Carnot Engine is given by

QH QC TH TC

QH
TH

The maximum efficiency of any engine operated between two temperatures is always
given by

TH TC
TH

as the efficiency of a reversible engine is maximum.

Efficiency of real engine is always less than that of reversible engine. If the engine is
irreversible then efficiency is calculated from

QH QC
QH

and not from temperatures.

For any irreversible engine,

dQH dQC TH TC

dQH
TH

dQC TC

dQH
TH

dQC dQH

TC
TH
Applying sign convention,

dQC dQH

0
TC
TH

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Thus for irreversible engine,

dQ
0
T

dQ
0
T

dQ
0
T

If the processes are all reversible, then

In general,

This is called Clausius inequality. The sum of dQ / T terms over a cycle is less than or
equal to zero depending upon whether the cycle is irreversible or reversible.
The changes in entropy are always determined using,

dS

dQRe v
T

1
p

Let A1B Represent irreversible process and A2B represent reversible process between
the same states.

dS

dQRe v
T

SAB

dQ

T
A2 B

dQ
T
A1B

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To determine entropy change we must have only reversible path. However the entropy
change between the states 1 and 2 is same regardless of the path as it is a state function.
What the above equation says is entropy is not equal to dQ/T along an irreversible path.
To determine entropy change for any irreversible path between two states, replace the
path by a reversible path with the same states, and find the entropy of the reversible path.

Entropy and irreversibility:


Let us look at a cyclic process given below.

1
p

Let A1B Represent reversible process and B2A represent irreversible process between
the same states. Therefore A2B is also irreversible. Since A1B is reversible,

SA1B

dQ
T
A1B

Since cycle as a whole is irreversible and as per Clausius inequality,

dQ
0
T

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dQ
dQ

0
T
T
A1B
B2 A

SA1B

dQ
0
T
B2 A

SB 2 A

dQ
0
T
B2 A

dQ
SB 2 A
T
B2 A

RHS is independent of the path which will be equal to SA1B .


LHS is dQ / T term and it is along an irreversible path and therefore it does not represent
entropy change.

Mathematical Statement of II law:


For a process involving transfer of heat Q from heat source at T1 to a heat sink at T2,

( S )total

Q Q

T1 T2

T T2
( S )total Q 1
T1T2

The process can be made less and less irreversible by lowering the temperature T1 closer
and closer to T2.
As the temperatures become closer and closer, irreversibility decreases and Stotal 0.
For any heat transfer there has to be some temperature difference. Therefore T1 > T2 and
hence,

Stotal 0.
This is the mathematical statement of II law of thermodynamics. Thus the entropy of the
universe always increases and the energy is conserved.

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Because of irreversibility, there will be some dissipation and degradation of energy which
will not be available as work. This is called lost work which is given by

Wlost T0 Stotal
Where T0 refers to the temperature of the sink to which heat is rejected.

etermination of entropy changes:


dS

dQR
T

This is the basic equation. The heat transfer term may replaced by any term using first
law or any equation applicable to the process for which entropy change is to be
determined. This is applicable only the process is reversible. For example, for an ideal
gas undergoing isothermal reversible process,

dQ dW pdV
pdV
dS
T
RdV
dS
V
V
S R ln 2
V1
This is how entropy changes may be determined

Fundamental Property Relations:


Apart from enthalpy, internal energy and entropy, there are other thermodynamic
properties which are necessary to apply to phase equilibria and reaction equilibria. So far
we have treated only closed systems which consist of single phase without any reaction.
In order treat the systems we need to know other energy terms involved with reaction and
phase equilibria. The use these properties will get clearer when we do the chapters on
these areas.

Let us derive the fundamental property relations from basics.

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Enthalpy:
From I law,

dU dQ dW
dU TdS pdV
H U pV
dH dU d(pV)
dU pdV Vdp
TdS pdV pdV Vdp
dH TdS Vdp

Helmholtz free energy:


It is defined as
A = U TS

Differentiating,

dA = dU-d(TS)
= TdS pdV TdS SdT
dA= - pdV SdT
Gibbs Free energy:
It is defined as G = H TS
Differentiating, dG= dH TdS SdT
= TdS +Vdp TdS SdT
dG = Vdp - SdT

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These four equations are called fundamental property relations as many equations are
derived from these equations.

Maxwells relations
As some of the thermodynamic properties are not directly measurable, we must write the
equations in terms of measurable properties. The measurable and determinable (by
experiment) properties are temperature, pressure, volume, heat capacities and in some
cases even enthalpies. These relations are derived from fundamental property relations.
The derivations are based upon a mathematical relation applied to exact differential
equations.
f
f
If z = f(x,y) then df dx dy
x y
y x

This equation is also written as


df = Mdx + Ndy
For this differential equation to be exact,
M

x x y

Applying these conditions to all the property relations, we get,

df Mdx Ndy

x x y

dU TdS pdV

T
p


V S
S V

dH TdS Vdp

T V

p S S p

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dA pdV SdT

p
S

T V V T

dG Vdp SdT

S
V


T p
p T

Generating function:
Consider

G
d
RT

RTdG Gd( RT )

R 2T 2

1
G
dG
dT
RT
RT 2

1
H TS
( Vdp SdT )
dT
2
RT
RT

Vdp SdT HdT SdT

RT
RT
RT 2
RT

V
H
dp
dT
RT
RT 2

G
d
RT

H
V
dp
dT

RT 2
RT

From this equation, at constant temperature and at constant pressure we can write,
( G / RT

( G / RT

)
V
RT ;
T
)
H
RT
p
2

If we know G/RT in terms of p and T, it can be used to evaluate other


thermodynamic properties and hence it is called generating function.

Entropy changes:

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Q
Q
We know that CP
; CV

T p
T V
Since dQ TdS ,
S
CP T

T p
C
S

P
T p T

And

S
CV T

T V
C
S

V
T V T

Using these,
T2

S p CP
T1

T2

T
dT
CP ln 2 and
T
T1

S V CV
T1

T
dT
CV ln 2
T
T1

If S is considered as
S = f (T,p) then
S
S
dS
dT dp
T p
p T

In this equation, the first partial derivative is replaced by CP/T which is derived and
second by a Maxwells relation, we get,

dS

CP
V
dT
dp
T
T p

Similarly by taking S as function of V and T, we get,

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dS

CV
p
dT
dV
T
T V

If there is any relation between three variables, from mathematics we have, a relation
between p, V and T as
V

p T


1
T T V V p

Using these relations, we can get,

dS

( V / T )p
CV
dT
dV
T
( V / p )T

( V / T )p

dU CV dT T
p dV
( V / p )T

Internal energy may also be written as

dU CP dT T
dp pdV
T p

Using dH TdS Vdp , we get

V
dH CP dT V T
dp
T p

Internal energy changes:


The internal energy changes can be expressed in terms measurable quantities such as heat
capacities, pressure, volume and temperature. We can use Maxwells relations to get
these expressions.
The following are fundamental property relations.

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dU TdS pdV
dH TdS Vdp
dA pdV SdT

dG Vdp SdT
We have derived the following relations.
dS

dS

dS

CP
V
dT
dp
T
T p
CV
p
dT
dV
T
T V

( V / T )p
CV
dT
dV
T
( V / p )T

p T


1
T T V V p

Let us derive the expression for internal energy in terms CP and CV.
dU TdS pdV

Replace dS in terms of CV,


( V / T )p
C

dU T V dT
dV pdV
( V / p )T
T

( V / T )p

dU CV dT T
p dV
(

V
/

p
)
T

Internal energy change in terms of Cp:


dU TdS pdV

Replace dS in terms of Cp,


C

V
dU T P dT
dp pdV
T p
T
V

dU CP dT T
dp pdV
T p

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Enthalpy changes:
Starting from

dH TdS Vdp
in the same way we can get,

V
dH CP dT V T
dp
T p

We can use these expressions and find the changes in enthalpy. These equations are
applicable for any gas. P-V-T relations used should be for the gas for which you are
determining the changes.
Use these relations and derive the expressions for dH and dU for ideal gas.

Effect of p, V and T on U, H and S:


S
V

T p
p T

This is one of the Maxwells relations which gives the effect of pressure on entropy at
constant temperature.
C
S

P
T
T p

This equation derived earlier gives the effect of temperature on entropy at constant
pressure.

( V / T )p

dU CV dT Vdp T
dV
( V / p )T

At constant volume,
Or

dU
CV
dT
U

CV
T V

This gives the effect of temperature on internal energy at constant volume.

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At constant temperature, since dT is zero,


( V / T )p

U
p

T
V T
( V / p )T

This gives the effect of volume of internal energy at constant temperature.


Similarly from

V
dH CP dT V T
dp
T p

we can get,
At constant pressure, H CP
T p

At constant temperature,

H
V

V T

T p
p T

These expressions give the effect of temperature and pressure on enthalpy.

Relationship between the heat capacities:


The heat capacities are related by the following expression.
V p
CP CV T

T p T V

which can also be written as


2

V p
CP CV T

T p V T

using the cyclic relation of partial derivatives of p, V and T.


1 V

;
V T p

1
V

are called Volume expansivity and isothermal Compressibility. The difference between
heat capacities is written in terms of these as

CP CV

2VT

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Effect of pressure and volume on heat capacities:


These are given by the following equations.
CP

2V

T
T 2
T

2V
CP

T
2
V T
T

p

V
T
p

2 p
CV

T
2

T
V T

CV

2 p V


T
T 2 p
T

The equation of state of a gas


is given by
V

RT
c

p T3

and the specific heat is given by


Cp a bT

Derive the expressions for changes in internal energy, enthalpy and entropy for an
isobaric process.
V

dU CP dT T
dp pdV
T p

As pressure is constant, dp = 0,
Internal energy:

dU CP dT pdV

dU ( a bT )dT pdV

U12 a( T2 T1 )

Enthalpy:

b
( T2 2 T1 2 ) p( V2 V1 )
2

V
dH CP dT V T
dp
T p

dH CP dT

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H12 a( T2 T1 )

dS

Entropy:

b
( T2 2 T12 )
2

CP
V
dT
dp
T
T p

dS

CP
dT
T

a bT
dS
dT
T

S1 2 a ln

T2
b( T2 T1 )
T1

A perfect gas is heated from 60 to 300oC at a constant pressure of 4 bar. The gas is then
cooled to 60oC at constant volume. The mass of the gas is 5 kg. Determine total entropy
change. CP and CV are 1.0 and 0.72 kJ/kg.K

pressure

T1

T2

3
volume

T2

S1 2

T1
T2

T1

dQ
T

C p dT
T

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ln

576
0.5479kJ / kg.K
333

T3

S2 3

T2

dQ

T3

T2

CV dT
333
0.72 ln
0.3945kJ / kg.K
576
T

S13 S12 S2 3
S1 3 0.5479 0.3945
0.2161kJ / kg.K

Total entropy change = 5(0.2161)=1.0805 kJ / K

Prove that

dU ( Cp pV )dT V ( p T )dp

Where

1
V

V
1 V

V T p
p T

U U(T , p )
U
U
dp
dU
dT

p
p T

dU TdS pdV

U
S
V

T
p

T p
T p
T p
dS

dQ
T

dS

C p dT
T

Cp
S

T
T

Equation (2) becomes


Cp
V
U
p

T
T

p
T p

dU TdS pdV
U
S
V

T
p

p T
p T
p T

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S
V


T p
p T

U
V
V

p
T p
p T
p T
Cp
dU T
T

V
V
p

dp
dT

T p
T p
p T

V
V
V
dp
C p p
dT T
p
T p

T p
p T
( Cp pV )dT ( TV pV )dp
dU ( Cp pV )dT V ( p T )dp

For ideal gas show that


U
U
U



0
p T V T S T
dU TdS pdV
U
V

T p

T
S T
T
U

T p
S T
p V

pV
R

T
V


p V R
V
U

T p 0

S
R

T
dU TdS pdV

U
S

T
p
V T
V T
p
S

T V V T
U
p

T
p

T
T V

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H U pV
U H pV
V

U
H


p
V

T
T
T

H
V

V T

T p
p T

U
V V

V T
p
T p p
p T

V
T

U
V
V

p
T p
p T
p T
U
R
RT

T p 2 0

p
p
p

And hence
U
U
U

V
T S T

Fugacity
It is derived from Latin, expressed as fleetness or escaping tendency. It is used to study
extensively phase and chemical reaction equilibrium.
We know that
dG VdP SdT -(1)
For isothermal condition
dG VdP
For ideal gases

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RT
P

RT
.dP
P
dG RTd ln P
dG

To find Gibbs free energy for an real gases.


pressure. Which we call fugacity(f).

True pressure is related by effective

dG RTd ln f -------(2)
Applicable for all gases (ideal or real)
On differentiation
G RT ln f
Is an constant depends on temperature and nature of gas.
fugacity has same units as pressure for an ideal gas.
For ideal Gases
dG VdP SdT
For Isothermal conditions
dG VdP
from equation (2)
RTd ln f VdP
V
d ln f
dP
RT

dp
p
d ln f d ln p
f p
Fugacity = Pressure for Ideal gases
d ln f

Fugacity coefficient ( ) : Fugacity coefficient ids defined as the ratio of fugacity of a


component to its pressure.
f

P
Is the measure of non ideal behavior of the gas.
Standard State: Pure gases, solids and liquids at temperature of 298k at 1 atmosphere are
said to exist at standard condition. The property at this condition are known as standard
state property and is denoted by subscripto.

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G o = Standard Gibbs free energy


f o = Standard fugacity

Estimation of fugacity for gases


I method
dG VdP SdT
For Isothermal conditions
dG VdP
from equation (2)
RTd ln f VdP
V
d ln f
dP
RT
Integrating the above equation with the limits 0 to f and pressure 1 to P

d ln f RT dP
1

Lower limit is taken as P =1 atm


At 1 atm assuming the gases expected to behave ideally

1
VdP
RT 1
if PVT relations are known , we can find fugacity at any temperature and pressure
ln f

II method
Using compressibility factor
dG VdP
RTd ln f VdP --------------(2)
V in terms of compressibility terms it is given as V

ZRT
P

Substitute V in equation 2
ZRT
RTd ln f
dP
p
d ln f Zd ln p
subtracting both sides by dlnP

d ln f d ln P Zd ln P d ln P

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d ln

f
( z 1)d ln P
P

d ln (Z 1)d ln P
Integrating the equation from 1 to and 0 to P

d ln (Z 1)d ln P
1

ln ( Z 1)
0

dP
P

Using generalized charts: using reduced properties a similar chart as compressibility chart
is predicted for fugacity.
f
Z 1
ln
dPr
P
Pr

Fugacity is plotted against various reduced pressure at various reduced temperature

Using Residual Volume(): The residual volume is the difference between actual
volume (V) and the volume occupied by one mole of gas under same temperature and
RT
RT
pressure V
, V
P
P

RT

dG
dP RTd ln f
P

dP

RT
dP
RTd ln f
P
RT

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f
dP d ln
RT
P
ln

dP
P
RT

Problem

For isopropanol vapor at 200oC the following equation is available


Z=1- 9.86 x 10-3P-11.45 x 10-5P2
Where P is in bars. Estimate the fugacity at 50 bars and 200 oC
PV
Z
1 9.86 10 3 P 11.41 10 5 P 2
RT

ZRT RT

(1 9.86 10 3 P 11.41 10 5 P 2 )
p
P
P

1
ln f
VdP
RT 1
1
ln f
RT
50

ln f

RT
(1 9.86 10 3 P 11.41 10 5 P 2 )dP
P
50

50

dp
3
5
1 p 1 9.86 10 dP 1 11.41 10 PdP

2
2
50
3
5 (50 1 )
ln f ln 9.86 10 50 1 11.41 10
2
1

f=26.744 bar
f 26.744

0.5348
P
50

Fugacity for liquids and solids


General expression for fugacity is
P
1
ln f
VdP
RT 1

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For solids and liquids at constant temperature the specific volume does not change
appreciably with pressure, therefore the above equation is integrated by taking volume
constant. Integrating the above equation from condition 1 to 2
f2
P
V 2
ln
f

f
P dP
RT
1
1

ln

f2
V
P2 P1

f1 RT

Problem:
Liquid chlorine at 25oC has a vapour pressure of 0.77Mpa, fugacity 0.7Mpa and Molar
volume 5.1x 10-2 m3/kg mole. What is the fugacity at 10 Mpa and 25oC

P1 0.77 10 6 Pa
f1 0.7 10 6 Pa

P2 10 10 6 Pa
ln

T 298K R 8314

J
Kgmole

f2
V
P2 P1

f1 RT

f=0.846Mpa

Activity(a):
It is defined as the fugacity of the existing condition to the standard state fugacity
f
a o
f
Effect of pressure on activity
The change in Gibbs free energy for a process accompanying change of state from
standard state at given condition at constant temperature can be predicted as

G RT ln f

G o RT ln f o

f
G G G o RT ln o RT ln a
f
at constant temperature dG VdP

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GO

dG V dP
Po

G V ( P P o ) RT ln a V ( P P o )
ln a

V
( P P o ) This equation predicts the effect of pressure on activity
RT

Effect of Temperature on Activity

G G G o RT ln a
G Go

T
T
Differentiating the above equation with T at constant P
Go
G


T
T
d ln a

T
dT P T

P
P
o
H
H
d ln a
R


2
RT
RT 2
dT P
R ln a

Ho H
d ln a
This equation predicts the effect of temperature on activity.
R

RT 2
dT P

Properties of solutions
The relationships for pure component are not applicable to solutions. Which needs
modification because of the change in thermodynamic properties of solution. The
pressure temperature and amount of various constituents determines an extensive state.
The pressure, temperature and composition determine intensive state of a system.

Partial Molar properties:

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The properties of a solution are not additive properties, it means volume of solution is not
the sum of pure components volume. When a substance becomes a part of a solution it
looses its identity but it still contributes to the property of the solution.
The term partial molar property is used to designate the component property when it is
admixture with one or more component solution.
A mole of component i is a particular solution at specified temperature and pressure has
got a set of properties associated with it like VP , S i etc . These properties are partially
responsible for the properties of solution and it is known as partial molar property
It is defined as
nM
Mi
ji

n
i

T , P ,n
j

M i = Partial molar property of component i.


M = Any thermodynamic property of the solution
n = Total number moles in a solution
ni=Number of moles of component I in the solution
This equation defines how the solution property is distributed among the components.
Thus the partial molar properties can be treated exactly as if they represented the molar
property of component in the solution.
The above expression is applicable only for an extensive property using
We can write

nM ni M i
M xi M i

ni
xi
n

xi=Mole fraction of component i in the solution.


Measuring of partial molar properties
To understand the meaning of physical molar properties consider a open beaker
containing huge volume of water in one mole of water is added to it, the volume increase
is 18x 10-6 m3 If the same amount of water is added to pure ethanol the volume increased
is approximately 14 x 10 -6m3 this is the partial molar volume of H2O in pure ethanol.
The difference in volume can explain the volume applied by water molecules depending
on water molecules surrounding to them. When water is added to large amount of
ethanol, ethanol molecules hence volume occupied surround all the water molecules will
be different in ethanol.

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If same quantity of water is added to an equimolar mixture of H 2O and ethanol, the


volume change will be different. Therefore Partial molar property change with
composition. The intermolecular forces also changes with change in thermodynamic
property.
Let Vw = Partial molar volume of the water in ethanol water solution

V w = Molar volume of pure water at same temperature and pressure

V t =Total volume of solution when water added to ethanol water mixture and allowed
for sufficient time so that the temperature remains constant
V t n w Vw

Vw

V t
n w

In a process a finite quantity of water is added which causes finite change in composition.
Vw = property of solution for all infinitely small amount of water.
Vw lim v0

V t V t

nw nw

Temperature pressure an number of moles of ethanol remains constant during addition of


water.
V t
Vw
nE- no of moles of ethanol

nw T , P ,n
E

The partial molar volume of component i


V t
Vi

ni T , P ,n i
j

Partial molar properties and properties of the solution


Consider any thermodynamic extensive property (Vi, Gi etc) for homogenous system can
be determined by knowing the temperature, pressure and various amount of constituents.
Let total property of the solution
M t nM
n n1 n2 n3
1,2,3 represents no of constituents
Thermodynamic property is a f T , P, n1 , n2 , n3 n j

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For small change in the pressure and temperature and amount of various constituents can
be written as
M t
M t
M t
M t
dM t
dP

dT

dn

dni
1

P T ,n
P p ,n
P T , p ,n ,n
P P ,T ,n i
2

At constant temperature and pressure dP and dT are equal to zero.


The above equation reduces to

M t
dM
dni

i 1 ni P.T , n
j i
dMt in terms of partial molar property
i n

dM t M i dni
i 1

M i is an extensive property depends on composition and relative amount of constituents.


All constituent properties at constant temperature and pressure are added to give the
property of the solution.
dM t M 1dn1 M 2 dn2 M 3 dn3

dM t M 1 x1 M 2 x2 M 3 x3 dn

M M 1 x1 M 2 x2 M 3 x3 n M 1n1 M 2 n 2 M 3 n 3
t

M t ni M i

Problem
A 30% mole by methanol water solution is to be prepared. How many m3 of pure
methanol (molar volume =40.7x10 -3 m3/mol) and pure water (molar volume =
18.068x10-6 m3/mol) are to be mixed to prepare 2m3 of desired solution. The partial molar
volume of methanol and water in 30% solution are 38.36x10 -6 m3/mol and 17.765x10 -6
m3/mol respectively.
Methanol =0.3 mole fraction
Water=0.7 mole fraction
Vt=0.3 x38.36x10-6+0.7x17.765x10-6
=24.025x10-6 m3/mol
For 2 m3soolution
2

83.246 10 3 mol
6
24.025 10
Number of moles of methanol in 2m3solution

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=83.246x103x0.3= 24.97x103 mol


Number of moles of water in 2m3solution
=83.246x103x07= 58.272x103mol
Volume of pure methanol to be taken
= 24.97x103 x 40.7x10-3 =1.0717 m3
Volume of pure water to be taken
= 58.272x103 x 18.068x10-6 =1.0529 m3

Estimation of Partial molar properties for a binary mixture :


Two methods for estimation
Analytical Method and Graphical Method(Tangent Intercept method)
Analytical Method: The general relation between partial molar property and molar
property of the solution is given by
M

M i M x k
k i x1
x K T , P ,n
k

For binary mixture


i 1, k 2

M 1 M x 2
x2 x1 1, x2 1 x1 , x2 x1
x 2 T , P
At constant Temperature and pressure
M
M 1 M (1 x1 )
x1

M
M 2 M x1
x1

------(a)

-----------(b)

The partial molar property (extensive property) for a binary mixture can be estimated
from the property of solution using above equations (a) and (b).

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Tangent Intercept method:


This is the graphical method to estimate partial molar properties. If the partial molar
property (M) is plotted against the composition we get the curve as shown in the figure.

Suppose partial molar properties of components required at any composition, and then
draw a tangent to this point to the curve. The intercept of the tangent with two axis x 1=1
and x1=0 are I1 and I2.
Slope of the tangent

M I 2 x1

dM
dx1

I 2 M x1

dM
dx1

dM M I 2

dx1
x1

Comparing I2 with equation (b) I 2 M 2

and also (right hand side)

I 1 M 1 x1

dM I 1 M

dx1
1 x1

dM
dx1

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I 1 M 1 x1

dM
Comparing with equation(a) I 1 M 1
dx1

The intercept of the tangent gives the partial molar properties.


Limiting cases: For infinite dilution of component when at x1=0 a tangent is drawn at

x1=0 will give the partial molar property of component 1 at infinite dilution ( M 1 ) and

tangent is drawn at x2=0 or x1=1 will give infinite dilution ( M 2 ) of component 2

M2

Problem
The Gibbs free energy of a binary solution is given by

G 100 x1 150 x2 x1 x2 (10 x1 x2 )

cal
mol

(a) Finnd the partial molar free energies of the components at x2=0.8 and also at infinite
dilution.
(b) Find the pure component properties

Sol: G 100 x1 150 x2 x1 x2 (10 x1 x2 )

cal
mol

Substitute x2 1 x1 and simplifying


G 9 x1 8x1 49 x1 150
3

G1 G (1 x1 )
x1

G
2
27 x1 16 x1 49
x1
G1 18x1 35x1 16 x1 101
3

G2 G x1
x1

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G2 18x1 8x1 150


3

To find the partial molar properties of components 1 and 2


x2=0.8,

x1=1-0.8 = 0.2

G1 18x1 35x1 16 x1 101


3

G1 102.944

cal
mol

G2 18x1 8x1 150


3

G2 149.824

cal
mol

At infinite dilution

G1 G1atx1 0

G1 101

G2
G2

cal
mol

G2 atx1 1 or x2=0

160

cal
mol

To find the pure component property


G1 G1atx1 1

G1 100

cal
mol

G2 G2 atx1 0

G1 150

cal
mol

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Chemical Potential:
It is widely used as a thermodynamic property. It is used as a index in chemical
equilibrium, same as pressure and temperature. The chemical potential i of component i
in a solution is same as its partial molar free energy in the solution G i
The chemical potential of component i

G t

i Gi

ni T , P ,n

G t f P, T , n1 , n2
i n
G t
G t
G t
dG
dni
dP
dT
i 1 ni T ,n
P T ,n
T P ,n
j
t

G t
G t
dG t
dP

dT i dni
P T ,n
T P ,n

For closed system there will be no exchange of constituents (n is constant)

dG t V t dP S t dT
at constant temperature

G
t
P V
T
at constant pressure

G
t
T S
P

dG t V t dP S t dT i dni

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At constant temperature and pressure

dG
t

T ,P

i dni

For binary solution G x1 1 x2 2

Effect of temperature and pressure on chemical potential


Effect of temperature:
We know that

G t

i Gi
-------------------(1)

ni T , P ,n
j

differentiating equation (1) with respect to T at constant P


2G
i
T Tdn ---------------------(2)

P ,n
i

dG VdP SdT ---------(3)

differentiating equation (3) with respect to T at constant P

G
T S
P
differentiating again w r t ni

S t
2G

Si

Tni
ni P ,n j
S i is partial molar entropy of component I

i
T

T


T i i

T2

P ,n

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T Si i
T2

G H TS

In terms of partial molar properties


Gi H i T S i

i H i T S i
H i i T S i

Hi
i

T
T2

P ,n

This equation represents the effect of temperature on chemical potential.


Effect of Pressure:
We know that

G t

i Gi
-------------------(4)

ni T , P ,n
j

differentiating equation (4) with respect to T at constant P


2G
i
P Pdn ---------------------(5)

T ,n
i

dG VdP SdT ---------(3)

differentiating equation (3) with respect to P at constant T

G
P V
T

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differentiating again w r t ni

V
2G

Vi ,

Pni ni T ,n
j
i
P Vi

T ,n
This equation represents the effect of pressure on chemical potential

Fugacity in solutions
For pure fluids fugacity is explained as

dG RTd ln f
lim P0

f
1
P

The fugacity of the component i in the solution is defined as analogously by


d i RTd ln f i

limP 0

Pi

i is Chemical potential
f i is partial molar fugacity
For ideal gases Pi yi PT
PT Total pressure.

Fugacity in Gaseous solutions


We know that

G t

i Gi
------(1)

ni T , P ,n
j

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differentiating equation (1) with respect to T at constant P


2G
i
-----(2)

T ,n Pdn i

dG VdP SdT -----(3)

differentiating equation (3) with respect to P at constant T

G
P V
T
differentiating again w r t ni

V
2G

Vi ,

Pni ni T ,n
j
i
P Vi

T ,n

i Vi P
RTd ln f i Vi dP
Vi
dP
RT
Subtracting both sides by d ln Pi
d ln f i

d ln f i d ln P i

Vi
dP d ln P i
RT

f V
d ln i i dP d ln P i
Pi RT

d ln Pi d ln P d ln yi

Composition is constant dln yi=0


The above equation can be written as

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dP
P

d ln Pi d ln P

Modifying equation (a)

d ln i

1
RT

RT

V i
P

dP

i - Represents fugacity of the component i in the solution.

Ideal solutions
An ideal mixture is one, which there is no change in volume due to mixing. In other
words for an ideal gaseous mixture partial molar volume of each component will be equal
to its pure component volume at same temperature and pressure.
and V Vi xi xiVi --- Raoults law
Ideal solutins are formed when similar components or adjacent groups of group are
mixed
Eg: Benzene-Toluene
Methanol- Ethanol
Hexane- Heptane
Solutin undergo change in volume due to mixing are known as non ideal solutions
Vi Vi
Eg: Methanol-Water
Ethanol-water.
Ideal solutions formed when the intermolecular force between like molecules and unlike
molecules are of the same magnitude.
Non-ideal solutions are formed when intermolecular forces between like molecules and
unlike molecules of different magnitude.
For ideal solutions
V t niVi -------------------(1)
Vi is the molar volume of pure component I
V t
Vi
T , P , n j Vi ----------------- (2)

n
i

The residual volume for the pure component is


RT
Vi
p

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Therefore we know from reduced properties


P
f
1
RT
ln i
Vi
dP ----(3)

P RT 0
P
For component i in terms of partial molar properties
P
f
1
RT
ln i
V i
dP ----(4)

P
Pi RT 0
Subtracting equation (3) from (4)
fi P

1
ln

f i Pi RT

V
P

Vi dP ----(5)

we know that Pi yi P
equation (5) reduces to
P
fi
1
ln

V i Vi dP
f i yi RT 0

comparing equation (2)


fi
1
f i yi
f i f i yi --Lewis Randal rule
Lewis Randal rule is applicable for evaluating fugacity of components in gas mixture.
Lewis Randal rule is valid for
1. At low pressure when gas behaves ideally.
2. When Physical properties are nearly same.
3. At any pressure if component present in exess.

Henrys Law
This law is applicable for small concentration ranges. For ideal solution Henrys law is
given as
f i xi k i

Pi xi k i
ki- Henrys Constant, f i -Partial molar fugacity,
Pi -Partial pressure of component i.

Non Ideal solutions


For ideal solutions f i xi k i ------------(a)

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For non ideal solutions f i i xi k i ----------(b)


Where i is an activity coefficient of component i.
Comparing equation (a) and (b)
f
i i Non ideal solution / Ideal solution
fi
For both ideal and Non ideal solutions the fugacity of solution is given by
equation
f
ln f xi ln i
xi

ln xi ln i

Problem:
A terinary gas mixture contains 20mole% A 35mole% B and 45mole% C at 60 atm and
75oC. The fugacity coefficients of A,B and C in this mixture are 0.7,, 0.6 and 0.9.
Calculate the fugacity of the mixture.
Solution:
ln x A ln A x B ln B xc ln c

ln 0.2 ln(0.7) 0.35 ln(0.6) 0.45 ln(0.9)


ln 0.2975
0.7426

f
,
P

f =44.558atm

Gibbs Duhem Equation


Consider a multi component solution having ni moles of component I the property of
solution be M in terms of partial molar properties
M t nM n M i -----------------------(1).
Where n is the total no of moles of solution
Differentiating eq (1) we get
d (nm) ni d M i M i dni ----------------------------(2)
We know that
nM f T , P, n1 , n2

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(nM )
(nM )
(nM )
(nM )
(nM )
dT
dP
dn1
dn2

T P ,n1 ,n2
P T ,n1 ,n2
n1 T , P1 ,n2.n3
n2 T , P ,n1 ,n3

(nM )
n( M )
n( M )
(nM )
dT

dP

dni

P
T P , n1 , n2

T , n1 , n2
ni T , P , n j
From the definition of partial molar properties

n( M )
n( M )
(nM )
dT

dP M i dni
P
T P ,n1 ,n2
T ,n1 ,n2

----------(3)

Subtracting equation (2) from equation (3)

n( M )
n( M )
dT
dP ni d M i 0 ------------------(4)
T
P T ,n1 ,n2
P ,n1 , n2
Equatin (4) is the fundamental form of Gibbs Duhem equation

Special Case
At constant temperature and pressure dT and dP are equal to zero. The equation becomes
xi d M i 0
For binary solution at constant temperature and pressure the equation becomes
x1d M 1 x2 d M 2 0
x1d M 1 (1 x1 )d M 2 0 ------------(5)

dividing equation(5) by dx1

x1

d M1
dM2
(1 x1 )
0
dx1
dx1

The above equation is Gibbs Duhem equation for binary solution at constant temperature
and pressure in terms of Partial molar properties.
Any Data or equation on Partial molar properties must satisfy Gibbs Duhem
equation.

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Problem:
Find weather the equation given below is thermodynamically consistent
G 100 x1 150 x2 x1 x2 (10 x1 x2 )

G1 G (1 x1 )

G2 G x1

G
x1

G
x1

G1 18x1 35x1 16 x1 101


3

G2 18x1 8x1 150


3

d G1
dx1

54 x1 70 x1 16
2

d G2
2
54 x1 16 x1
dx1
G D equation

x1

d M1
dM2
(1 x1 )
0
dx1
dx1

x 1 ( 54 x 1 70 x 1 16 ) ( 1 x1 )( 54 x 1 16 x 1 ) 0
2

It satisfies the GD equation, the above equation is consistent.

Phase Equilibrium
Criteria for phase equilibrium: If a system says to be in thermodynamic equilibrium,
Temperature, pressure must be constant and there should not be any mass transfer.
The different criteria for phase equilibrium are
At Constant U and V: An isolated system do not exchange mass or heat or work with
surroundings. Therefore dQ=0, dW=0 hence dU=0. A perfectly insulated vessel at
constant volume dU=0 and dV=0.

dSU ,V 0
At Constant T and V: Helmoltz free energy is given by the expression
A U TS
U A TS
on differentiating
dU dA TdS SdT
we know that

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dU TdS PdV
TdS PdV dA TdS SdT
dA PdV SdT

Under the restriction of constant temperature and volume the equation simplifies to

dAT ,V 0
At Constant P and T
The equation defines Gibbs free energy
G H TS
G U PV TS
dG dU PdV VdP TdS SdT
dU dG PdV VdP TdS SdT
dU dG dG PdV TdS
Under the restriction of constant Pressure and Temperature the equation simplifies to

dGT , P 0
This means the Gibbs free energy decreases or remains un altered depending on the
reversibility and the irreversibility of the process. It implies that for a system at
equilibrium at given temperature and pressure the free energy must be minimum.

Phase Equilibrium in single component system


Consider a thermodynamic equilibrium system consisting of two or more phases of a
single substance. Though the individual phases can exchange mass with each other.
Consider equilibrium between vapor and liquid phases for a single substance at constant
temperature and pressure. Appling the criteria of equilibrium
dG 0

dG a dG b 0
dG a and dG b are chane in free energies of the phases a and b respectively.
We know that
dG VdP SdT Gi dni
For phase a
dG a V a dP a S a dT a G a dn a
For phase b
dG b V b dP b S b dT b G b dn b

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At constant temperature and pressure


dG a G a dn a , dG b G b dn b
For a whole system to be at equilibrium
dn a dn b 0

or
dn a dn b

G b dn a 0

Ga Gb
When two phases are in equilibrium at constant temperature and pressure, Gibbs free
energies must be same in each phase for equilibrium.
RT ln f a C RT ln f b C
fa fb

Clapeyron Clausius Equation


Clapeyron Clausius Equation are developed two phases when they are in equilibrium
(a) Solid- liquid
(b) Liquid-Vapor
(c) Solid Vapor
Consider any two phases are in equilibrium with each other at given temperature and
pressure. It is possible to transfer some amount of substance from one phase to other
in a thermodynamically reversible manner(infinitely slow).The equal amount of
substance will have same free energies at equilibrium .
Consider GA is Gibbs free energy in phase A and GB is Gibbs free energy in phase B
at equilibrium.
GA=GB ------(1)
G = GA -GB =0 ------(2)
At new temperature and pressure the free energy / mole of substance in phase A is
G A dG A for Phase B G B dG B
From basic equation
dG VdP SdT -----(3)

dG A V A dP S A dT
dG B VB dP S B dT

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V A dP S A dT VB dP S B dT
dPVB V A dT S B S A
dP S

dT V
V represents the change in volume when one mole of substance pases from
phase A to Phase B
Q
S
T
dP
Q

dT TV

dP
Q
----(4)

dT T V B V A
This is a basic equation of Clapeyorn Clasius equation.
BVapor state A- Liquid state
Q=molar heat of vaporization = H V
VB is molar volume in vapor state, VA is molar volume in liquid state,
dP
Q

dT T V g Vl

Vg>>>Vl (Gas volume is very high when compared to liquid volume)

dP H V

dT TV g

HV (Latent heat of vaporization), V g

RT
P

dP
P

dT TRT
dP dT

P
RT2

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Integrating the above equation from T1to T2 and pressure from P1 to P2.

dP 2 dT
P P R T T
1
1

P2

P 1
1
ln 2
P1 R T1 T2
This equation is used to calculate the vapor pressure at any desired temperature.

Problem:

The vapor pressure of water at 100oC is 760mmHg. What will be the vapor pressure
at 95oC. The latent heat of vaporization of water at this temperature range is
41.27KJ/mole.
P1 760 mmHg T1 100 273 373 K

P2

T2 95 273 368 K

P 1
1
ln 2
P1 R T1 T2

P 41.27 10 3
ln 2
8.314
760

1
1
373 368

P2 634.3mmHg

Phase Equilibrium in Multi component system


An heterogeneous system contains two or more phases and each phase contains two or
more components in different proportions. Therefore it is necessary to develop phase
equilibrium for multi component system in terms of chemical potential.
The partial molar free energy or chemical potential is given as
G
i Gi
ni T , P ,n
j

For a system to be in equilibrium with respect to mass transfer the driving force for
mass transfer( Chemical potential) must have uniform values for each component in
all phases.

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Consider a heterogeneous system consists of phase


, , and
containing various components 1,2,3-------C , that constitutes the system.
k
The symbol i represents chemical potential of component iin phase k.
At constant temperature and pressure, for the criterion for equilibrium is
dG=0 ----(1)
Free energy for multi component system given by the expression
dG VdP SdT i dni ------(2)
At constant Temperature and pressure
dG i dni ----(3)
Comparing equation 1 and 3
0 i dni
For multi component system
C


i 1 k

k
i

dni 0
k

Expanding the above equation


1 dn1 1 dn1 1 dn1 1 dn1

2 dn2 2 dn2 2 dn2 2 dn2

-----(4)

c dnc c dnc c dnc c dnc 0


Since the whole system is closed it should satisfy the mass conservation equation

dn1 dn1 dn1

dn2 dn2 dn2

----(5)

dnC dnC dnC 0

The variation in number of moles dni is independent of each other. However the sum of
change in mole in all the phases must be zero. For the criterion of equilibrium is that the
chemical potential of each component must be equal in all phases.

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1 1 1
2 2 2

C C C
At constant temperature and pressure the general criterion for thermodynamic
equilibrium in closed system for heterogeneous multi component system
At constant T and P

i
i

for i=1,2,3--------C

Since i Gi RT ln f i
The above equation is also satisfied in terms of fugacity

fi fi fi

for i=1,2,3--------C

Phase Diagram for Binary solution


Constant pressure equilibrium
Consider a Binary system made up of component A and B. Where it is assumed to be
more volatile than B where vapour pressure A is more than B. When the pressure is
fixed at the liquid composition can be changed the properities such as temperature and
vapour compositions get quickly determined VLE at constant pressure is represented on
T-xy diagram.
Boiling point diagrams
When temperature is plotted against liquid(x) and vapour(y) phase composition. The
upper curve gives and lower curve gives. The lower curve is called as bubble point
curve and upper curve is called as Dew point curve. The mixture below bubble point is
sub cooled liquid and above the Dew point is super heated vapour. The region between
bubble point and Dew point is called mixture of liquid and vapour phase.

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Consider a liquid mixture whose composition and temperature is represented by


point A. When the mixture is heated slowly temperature rises and reach to point B,
where the liquid starts boiling, temperature at that point is called boiling point of whether
heating mixture reaches to point G when all liquids converts to vapour the temperature
at that point is called as Dew point. Further heating results in super heated vapour. The
number of tic lies connects between vapour and liquid phase. For a solution the term
boiling point has no meaning because temperature varies from boiling point to Dew point
at constant pressure.

Effect of pressure on VLE


The boiling point diagram is drawn from composition x=0 to x=1, boiling point of pure
substances increases with increase in pressure. The variation of boiling point diagrams
with pressure is as shown in diagram. The high pressure diagrams are above low
pressure.

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Equilibrium diagram
Vapor composition is drawn against liquid comp at constant pressure. Vapour is always
rich in more volatile component the curve lies above the diagonal line.

Constant temperature Equilibrium


VLE diagram is drawn against composition at constant temperature. The upper curve is
and lower curve is drawn at vapour comp(y). Consider a liquid at known pressure and
composition at point A as the pressure is decreases and reaches to point B where it
starts boiling further decreases in pressure reaches to point C when all the liquid
converts to vapour, further decreases in pressure leads to formation of super heated
vapour. In between B to C both liquid and vapour exists together

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Non ideal solution


An ideal solution obeys Raoults law and p-x line will be straight. Non ideal solution do
not obey Raoults law. The total pressure for non ideal solutions may be greater or lower
than that for ideal solution. When total pressure is greater than pressure given by Raoults
law, the system shows positive deviation from Raoults law.
Eg: Ethanol-toluene
When the total pressure at equilibrium is less than the pressure given by Roults law the
system shows negative deviation from Raoults law.
Eg: Tetrahydrofuron-ccl4

Azeotropes
Azeotropes are constant boiling mixtures. When the deviation from Raoults law is very
large p-x and p-y curve meets at this point y1=x1 and y2=x2
A mixture of this composition is known as Azeotrope. Azeotrope is a vapour liquid
equilibrium mixture having the same composition in both the phases.

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Types of Azeotropes
Azeotropes are classified into two types
1. Maximum curve pressure, minimum boiling azeotropes
2. Minimum pressure maximum boiling azeotrope
The azeotrope formed when negative deviation is very large will exhibit minimum
pressure or maximum boiling point, this is known as minimum pressure Azeotrope.
Eg : Ethanol water, benzene-ethanol
The azeotrope formed when ue deviation is very large will exhibit minimum pressure or
maximum boiling point, this is known as minimum pressure azeotrope.
Phase diagram for both types of Azeotropes
Minimum Temperature azeotropes

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Maximum Tem Min pressure Azeotropes

Calculation of VLE for ideal solution


Ideal solution: Ideal solution is one which obeys Raoults law. Raoults law states that the
partial pressure is equal to product of vapor pressure and mole fraction in liquid phase.

PA PVA x A
PA- Partial pressure

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PVA- Vapor pressure


xA- Mole fraction of component A
For binary solution (For component A and B)
We know that PT PA PB -------(1)

PA PVA x A , PB PVB x B
Substitute PA and PB in equation 1
PT PVA x A PVB x B
1 x A xB , 1 x A xB
PT PVA x A PVB (1 x A )
PT PVA PVB x A PVB --------(2)
P PVB
xA T
PVA PVB
Assuming the vapor phase is also ideal

PA PVA x A

PT
PT
Substituting PT from equation (2)
yA

yA

PVA x A
PVA PVB x A PVB

Dividing numerator and denominator by PVB

PVA
xA
PVB
yA
PVA

1 x A 1
PVB

yA

x A

1x A 1

The above equation relates x and y


is known as relative volatility of component A with respect to component B

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Problem: The binary system acetone and acetone nitrile form an ideal solution. Using
the following data prepare
P-x-y diagram at 50oC
T-x-y diagram at 400mm Hg
x-y diagram at 400 mm Hg
T
38.45
42
46
50
54
58
62.3

PV1
400
458.3
532
615
707.9
811.8
937.4

PV2
159.4
184.6
216.8
253.5
295.2
342.3
400

Solution: PT PV 1 PV 2 x1 PV 2 , y A
x1
0.0
0.2
0.4
0.6
0.8
1.0

PT
253.5
325.8
398.1
470.4
542.7
615

PV 1 x1
, PV1= 615, PV2 = 253.5
PT

y1
0.0
0.377
0.6179
0.784
0.906
1

T-x-y diagram at 400 mm Hg , PT=400mmHg x1


T
PV1
PV2
x1
38.45 400
159.4
1
42
458.3
184.6
0.7869
46
532
216.8
0.5812
50
615
253.5
0.405
54
707.9
295.2
0.2539
58
811.8
342.3
0.122
62.3 937.4
400
0
Calculation of VLE for non Ideal solution

PT PV 2
P x
, y A V1 1
PV 1 PV 2
PT

y1
1
0.9015
0.7729
0.6226
0.449
0.2475
0

For non ideal solution


Partial pressure is given by Pi i xi PVi

i - Activity coefficient

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xi- Mole fraction


PVi vapor pressure
For binary mixture

P1 1 x1 PV 1
P2 2 x2 PV 2

PT P1 P2
PT 1 x1 PV 1 2 x2 PV 2

1 x1 PV 1
P1

PT 1 x1 PV 1 2 x 2 PV 2

1
x P
1 2 2 V2
1 x1 PV 1
The above equation relates x and y for non ideal solution
y1

Activity coefficients are functions of liquid composition x, many equations are available
to estimate them. The important equations are

Vanlaar equation
Wilson equation
Margules Equation

Vanlaar Equation:
Estimation of activity coefficient
2
Ax 2
ln 1
2
A

x
2
B 1

ln 2

Bx1

x1 A x 2

Where A and b are known as vanlaar constants, if the constants are known the
activity coefficients can be estimated.
Estimation of Vanlaar constants
1st Method: If the activity coefficients are known at any one composition, then vanlaar
constants A and B can be estimated by rearranging the equation

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x ln 2
A ln 1 1 2

x1 ln 1

x ln 1
B ln 2 1 1

x 2 ln 2

2nd Method
For a systems forming azeotrope, if the temperature and pressure s are known at
azeotropic composition then activity coefficients can be calculated as shown below.

P1 x1 1 PV 1
PT y1 x1 1 PV 1
At azeotrpic composition x1=y1
PT
PT
1,
2
PV 1
PV 2
Van laar constants A and B can calculated using the above equations.

Problem: The azeotope of ethanol and benzene has composition of 44.8mol% C2H5OH at
68oC and 760mmHg.At 68oC the vapor pressure of benzene and ethanol are 517 and 506
mmHg.
Calculate
Vanlaar constants
Prepare the graph of activity coefficients Vs composition
Assuming the ratio of vapor pressure remains constant, prepare equilibrium
diagram at 760mmHg.
Solution:
At azeotropic composition x1=y1=0.448,
PV2 =517mmHg

PT
1,
PV 1

x2=y2=0.552,

PV1=506mmHg,

PT
2
PV 2

760
1 1.501 ,
506

x ln 2
A ln 1 1 2

x1 ln 1

760
2 1.47
517
2

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(0.552) ln(1.47)
A ln(1.501) 1

(0.448) ln(1.501)

A=0.829

x ln 1
B ln 2 1 1

x 2 ln 2

(0.448) ln(1.501)
B ln(1.47) 1
(0.552) ln(1.47)

B=0.576
Make use of the equations given below for plotting graph of activity coefficients Vs
composition.

ln 1

y1

Ax 2

B x1 x 2

, ln 2

1 x1 PV 1
P1

PT 1 x1 PV 1 2 x 2 PV 2

x1
0
0.2
0.4
0.6
0.8
1.0

x2
1
0.8
0.6
0.4
0.2
0

Bx1

x1 A x 2

1
x P
1 2 2 V2
1 x1 PV 1

6.745
2.4
1.644
1.21
1.0112
1

1
1.095
1.374
1.721
2.618
3.723

y1
0
0.384
0.4384
0.5077
0.609
1

Margules equation
Eetimation of activity coefficients
2
ln 1 x2 A 2B Ax1
ln 2 x1 B 2A Bx2
2

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The constant A in the above equation is terminal value of ln1 at x1=0 and constant B is
the terminal value of ln2 at x2=0
When A=B
2
2
ln 1 Ax 2 , ln 2 Ax1
The above equations are known as Margules suffix equation.
Wilson Equation:
Wilson proposed the following equation for activity coefficients in binary solution
12

21
ln 1 lnx1 12 x2 x2

x1 12 x2 21 x1 x2
12

21
ln 2 lnx2 21 x1 x1

x1 12 x2 21 x1 x2

Wilson equation have two adjustable parameters 12 and 21 . These are related to pure
component molar volumes.

12

V2
11 V2
a
exp 12
exp 12

V1
RT V1

RT

V1
22 V1
a
exp 12

exp 21

V2
RT V2

RT
V1 and V2 molar volumes of pure liquids
- Energies of interaction between molecule
Wilson equation suffers main disadvantages which is not suitable for maxima or minima
on ln versus x curves.
Consistency of VLE data
Gibbs duhem equation in terms of thermal consistency

21

x1

d ln 1
d ln 2
(1 x1 )
0
dx1
dx1

Plot of logarithmic activity coefficients Vs x1 of component in binary solution

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According to Gibbs Duhem equation both slopes must have oppsite sign then only the
data is consistent, otherwise it is inconsistent.
For the data to be consistent it has satisfy the following condition.
1. If one of ln curves has maximum at certain concentration and the other curve
should be minimum at same composition.
2. If there is no maximum or minimum point both must have + ue or ue on entire
range.

Co-existence equation
The general form of Gibbs duhem equation at constant temperature and pressure
xi d M i 0 ---(1)
In terms of partial molar free energies
xi d Gi 0 ------(2)
dividing equation (2) by dx1

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d Gi
0 -----(3)
dx1

Gi RT ln f i
at constant temperature
d Gi RT ln f i
----(4)

dx1
dx1
substituting equation (4) in equation (3)

x
x

RT ln f i
0
dx1
d ln f i
0 ------(5)
dx1

For binary system


d ln f1
d ln f 2
x1
x2
0 ----(6)
dx1
dx1
x1d ln f1 x2 d ln f 2 0 -----(7)

Equation (5) (6) and (7) are Gibbs Duhem equation in terms of fugacites and thus
applicable for both liquid and vapor phase

For liquids
f i i xi f i
ln f i ln i ln xi ln f i

differentiating with respect to x1

=0

d ln f i d ln i d ln xi d ln f i
-------(8)

dx1
dx1
dx1
dx1

fi is a pure component ffugacity it does not vary with x1


Substituting equation (8) in equation (5)

d ln
d ln x
xi dx i xi dx i 0
1
1

=0

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d ln i
0 ----------------(9)
dx1

For binary system


d ln 1
d ln 2
x1
x2
0 ---------(10)
dx1
dx1

x1d ln 1 x2 d ln 2 0 -----------(11)
Equation (9) (10) and (11) are Gibbs Duhem equation in terms of activity coefficients
For ideal vapor
f i Pi
From equation 5

d ln Pi
0 ------------(13)
dx1
For binary system

x1

d ln P1
d ln P2
x2
0 ----------(14)
dx1
dx1

x1d ln P1 x2 d ln P2 0 ---------------(15)
Equation (13) (14) and (15) are Gibbs Duhem equation in terms Partial pressure.
For ideal vapor

P1 y1 PT , P2 y 2 PT
x1d ln( y1 PT ) x2 d ln( y2 PT ) 0
x1d ln y1 x1d ln y2 ( x1 x2 )d ln PT 0
x1 x2 1

x1d ln y1 x1d ln y 2 d ln PT 0
dP
x1 d ln y1 x2 d ln y 2
P

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dy
dy
dP
x1 1 x2 2
P
y1
y2
y 2 y1 0 , dy 2 dy1
on simplification

x (1 x1 )
dP
dy1 1

P
(1 y1 )
y1

Further simplification
y x
dP
P 1 1
dy1
y (1 y1 )
This is known as coexistence equation. It relates P,x,y for binary VLE system. This
equation is used to rest consistency of VLE data.

Consistency test for VLE data

x1d ln 1 x2 d ln 2 0
d ln 2

x1 d ln 1
x2

d ln 2

x1 d ln 1
(1 x1 )

d ln 2

x1 d ln 1
(1 x1 )

Redlich Kister Test


The excess free energy of mixing for a solution is given as
G e Gideal GNonideal
G e RT xi ln i

For binary system


G e RT x1 ln 1 x2 ln 2
differentiating with respect to x1

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d ln 1
d ln 2
dx
dG e
RT x1
ln 1 x2
ln 2 2
dx1
dx1
dx1
dx1

From Gibbs Duhem Equation


d ln 1
d ln 2
x1
x2
0
dx1
dx1

dx
dG e
RT ln 1 ln 2 2
dx1
dx1

dx2 dx1

dG e
RT ln 1 ln 2
dx1

dG e
RT ln 1
dx1
2
x1 1

dG

x1 0

RT

x1 1

1
ln dx1
2
x1 0

The two limits indicates pure component for which G e 0 , where LHS is zero for both
limits.
We can write
x1 1

0 ln 1 dx1
2
x1 0
This can be checked graphically. Net area should be equal to zero for
consistency(Area=0).

Problem
Verify whether the following data is consistent

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X1
0
0.2
0.4
0.6
0.8
1.0
Solution:

1
0.576
0.655
0.748
0.856
0.950
1.00

2
1.00
0.985
0.930
0.814
0.626
0.379

We know that the Redlich kister test is


x1 1

0 ln 1 dx1
2
x1 0

1
2

1
2

ln

0.576
0.665
0.804
1.052
1.518
2.639

-0.552
-0.408
-0.218
0.051
0.417
0.97

Plot ln

1
Vs x1
2

\
Area under the curve is zero. Data is consistent.

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CHEMICAL REACTION EQUILIBRIUM


Energy change accompanies all chemical reactions. Because of this energy
change the temperature of the products may increase or decrease depending on the
exothermic or endothermic nature of the reaction. The energy change may be
expressed in terms of heat of reaction, heat of combustion and heat of formation.
Heat of reaction is the change in enthalpy of a reaction under pressure of 1.0
atmosphere, starting & ending with all materials at a constant temperature T
Heat of combustion is the heat of reaction of a combustion reaction.
Heat of formation is the heat of reaction of a formation reaction. A formation
reaction is one which results in the formation of one mole of a compound from the
elements.
Eq.

H2 + O2 H2O
C +O2 CO2
C + H2 + 1/2 Cl2 CHCl3

The standard heat of reaction, standard heat of formation, and standard heat of
formation are respectively the heat of reaction, heat of combustion and heat of formation
under 1 atmosphere starting and ending with all materials at constant temperature of
250C.
In chemical industries, processes are carried out under isothermal conditions
and this requires the addition or removal of heat from the reactor. Heat of reaction
values will give the amount of heat to be removed or added. Knowing of this heat
value helps to design the heat exchange equipment.
Standard heat of reaction
Calculation of H298 form heats of formation data:
The standard heat of reaction accompanying any chemical change is equal to
the algebraic sum of the standard heats of formation of products minus the
algebraic sum of the standard heat of formation of reactants.
Hr = Hf 298 products - Hf 298 reactants
Heat of formation of any clement is zero

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Heat effects of chemical Reaction:


aA + bB cC + dD

For the reaction,

Let heat capacity be Cp = + T + T2

then we have CpA = A + AT + AT2


CpB = B + BT + BT2
CpC = C + CT + CT2
CpD = D + DT + DT2

And H0298 be standard heat of reaction at 298 K and standard heat of reaction at any
other temperature can be found by Kirchoffs rule
Cp

Cp

products

d H o
dT

where

Cp

reac tan ts

Cp cCpC dCpD aCpA bCpB then substituting the values of C , C , and C , C


pC
pD
pA
pB

= [c(C + CT + CT2) + d( D + DT + DT2 ) ] - [a (A + AT + AT2 ) + b (B + BT +


BT2 )]
= [(c C +d D ) (a A + b B ) ]+ [ (c C + d DT) (a A + b B)]T + [ c C + dD )
(a A+ b B )] T2

or

Cp = + T + T2

Pr oducts

Re ac tan ts

cCC dCD aCA bCB


Pr oducts

Pr oducts

Re ac tan ts

Re ac tan ts

Substituting in Kirchoffs rule

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H 0 T T T 2
H 0

H298

d
H 0
dT

H o T

T T
2

298

2 3
T
T I
2
3

H o T

OR in general

2 3
T
T I
2
3

H 0 CP dT
=T

T T dT
2

2 3
T
T I
2
3

A chemical reaction proceeds in the direction of decreasing free energy.The sum of the
free energies of the reactants should be more than the sum of energies of products. For a
reaction to take place

GRe action

products

or GRe action 0

reaction

Therefore G should be less than zero for a reaction to occur. When equilibrium is
reached free energies of the reactants equal free energies of products,. Therefore the
criterion for reaction equilibrium is G = 0
GReaction Calculation: Consider the reaction
Let

aA + bB cC + dD

GA , GB , GC , and GD be the partial molar free energies of A,B,C, and D in the

reaction mixture.

GA GA0 RT ln

fA
f

0
A

but

fA
fA0

aA the activity of A

GA GA0 RT lnaA
GB GB0 RT lnaB
GC GC0 RT lnaC
GD GD0 RT lnaD

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GRe action

products

Re ac tan ts

cGC dG D aGA bG B

= c GC0 RT lnaC d GD0 RT lnaD

a GA0 RT lnaA b GB0 RT lnaB

cGC dGD aGA bGB


RT
GRe action

lna

ac ad
At equilibrium G = 0 and K Ca Db
a a
A B

ac ad
D
0 G RT ln C
a
a ab
A
B

lnaD lnaA lnaB

ac ad
D
G RT ln C
a
a ab
A
B

K is equilibrium constant of the reaction

G0 RT ln K at equilibrium

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EFFECT OF TEMPERATURE ON EQUILIBRIUM CONSTANT K


Gibbs

Helmoholtz

equation

at

constant

pressure

is

given

G o
d

T H
2 but G o RT ln K
dT
T

RT
ln
K

d R ln K H
T

H
2 or
2
dT
dT
T
T
d ln K
H

Van't Hoff equation.


dT
RT 2
This may be integrated to find the effect of temperature on K
K2

T2

K1

T1

d lnK RT

When H is contant

dT

K2
H 1 1


K1
R T2 T1
if K1 is known at T1 , then K 2 can be calculated at other T2
ln

When H varies with T

d ln K

H 0
dT
RT 2
I
T
d ln K

dT
2
RT 2R 3R RT

ln K =

ln T T T 2
I

M
R
2R
6R
RT

Where M is a consatnt of integration

G 0 RT ln K
ln T T T 2

I
G 0 RT

M
R
2R
6R
RT

2
3
T
T
G 0 T ln T

I MRT
2
6
For the reasction C2H4 + O2 C2H4O, develop equations for H0, K, and G0, find
G0 at 550 K
Cp (Cal / mol K) Data:

C2H4

= 3.68 + 0.0224 T

O2

= 6.39 + 0.0021 T

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C2H4O = 1.59 + .00332 T


H0298

Standard heat of reaction


C2H4O = - 12 190 and C2H4

= - 12 500, Cal / mol


G0298 = -19070 Cal / mol

And

H Re action

298

Pr oducts

Re ac tan ts

= 1(-12190) 1( -12500) = 310 Cal / mol

In this problem Cp T

Pr oducts

Re ac tan ts

= 1.59 3.68 6.39 5.285


2

Pr oducts

1
2

= 0.0332 0.0224 0.0021 0.00975

Re ac tan ts

Then the variation of standard heat of reaction with temperature is


2 3
0.00975 2
T T I 5.285 T
T I
2
3
2
0.00975 2
0
Given H298
=310 = 5.285 T
T I
then I = 1452
2
0.00975 2
0
H o 5.285T
T 1452
This is variation of H298
with temparature
2

I
5.285
0.00975
1452
lnK =
ln T T T 2
M =
ln T
T
M
R
2R
6R
RT
2
2(2)
2T
H o T

G0298
19070
but G RT ln K 298
or lnK 298

32
RT
2(298)
5.285
0.00975
1452
32 =
ln 298
298
M
therefore M = 48.763
2
2(2)
2(298)
5.285
0.00975
1452
lnK =
ln T
T
48.763
2
4
2T
G0 RT ln K 2T ln K
0
298

0.00975
1452
5.285

2T ln K 2T
ln T
T
48.763
4
2T
2

0
3
2
G 5.285T ln T 4.875(10 )(T ) 1452 97.526(T )
G0550 5.285(550)ln550 4.875(10 3 )(550)2 1452 97 .526(550)
G0550 35320.62 Cal / mol

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50 mol% each of SO2 and O2 is fed to a converter to form SO3.


Show the variation of

i) Standard heat of reaction with T ii) Equilibrium constant

with T. The Hf and Gf at

298 K are

Hf

Gf

Component k Cal / k k Cal / k

SO2
O2
SO3

mol

mol

-70960

-71680

-94450

-88590

CP data:
Component a

b(103)

SO2

7.116

9.512

O2

6.148

3.102

SO3

6.0377 23.537

Feed contains 50 mole% SO2 and O2.This means for every one mole SO2 there will be
one mole O2 in the reactant side and mole O2 in the product side, according to SO2 +
O2 SO3
Reactants: 1 mol SO2 + 1 mol O2

Pr oducts

reac tan ts

= 6.0377 +

Products: 1 mol SO3 + mol O2 (excess)

1
6.148 7.116 6.148 - 4.152
2

1
= 23.53(10-3 ) + 3.102(10 3 ) - 9.512 (10 -3 ) + 3.102 (10-3 ) =12.474 x10 -3
2
Pr oducts
reac tan ts
2 3
0
H T
T
T I
2
3
12.474x10 -3 2
= -4.152T+
T I
2
0
But H 0 at 298 is given by H 298
H 0 H 0 94450 70960 23490 k Cal / k mol

products

Re ac tan ts

-23490=-4.152 (298 ) + 6.237 x 10 (298) I


I = -22818.19
-3

H 0 4.152 T 6.237 x10 3 T 2 22818.19


Next for K we have

I
lnK=
ln T
T
T
M
R
2R
6R
RT
4.152
12.474 x10 3
22818.19
lnK=
ln T
T
M
2
2 xR
2T

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We have

G0298 =

Products

lnK 298 =

G0298 = -RT ln K 298

G -

or lnK 298 =

G0298
2(298)

G = - 88590 - (- 71680) = - 16910 k Cal / k mol

Reactants

16910
28.372
2(298)

4.152
12474 x10 3
22818.19
ln 298
298
M
2
2x 2
2 x 298
M 0.9842
28.372

ln K 2.076lnT 3.1185 x10 3T

11409.09
0.9842
T

Derive the general equation for the standard free energy formation for N 2 + 3/2
H2 NH3
The absolute entropies in ideal gas state at 298 K and 1.0 atm are
NH3 = 46.01 g Cal / g mol K

298

N2

= 45.77

H2

= 31.21

(g Cal / g mol) = - 11040

Heat capacity Data is given by Cp= a + bT + cT2 the values are


Component

bx102

cx105

NH3

6.505

0.613

0.236

N2

6.903

- 0.038

0.193

H2

6.952

- 0.46

0.096

Compute the free energy change at 1500K. Is reaction feasible?

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We have G0 H o S 0 and S298

Pr oducts

G0298

Re ac tan ts

3
1

=46.01 (45.77) + (31.21) = 23.69 g Cal / g mol K


2
2

11040 298( 23.69) 3980.38 g Cal / g mol K


3
1

6.505 (6.903) 6.952 7.3745


2
2

Pr oducts
Re ac tan ts
3
1

b b b 0.613 x102 (0.038 x102 ) ( 0.046 x10 2 ) 7.01x10 3


2
2

Pr oducts
Re ac tan ts
a

Pr oducts

Re ac tan ts

3
1

0.236 x105 (0.193 x105 ) (0.096 x10 5 ) 0.045 x10 6


2
2

b 2 c 3
0
H298
aT
T
T I
2
3
7.01X 10 3
0.045 X 10 6
11040 ( 7.3745)298
298 2
( 298)3 I
2
3
a
b
c 2
I
ln K
ln T
T
T
M
and R =2 gCal / g mol K
R
2R
6R
RT

0
G298
RT ln K 298

6.6784

or ln K 298 =

OR

I = -9153.26

-3980.38
= 6.6784
-(2x298)

7.3745
7.01x10 3
0.045 x10 6
9153.26
ln 298
298
(298)2
M
2
2x 2
6x2
2 x 298
M 11.7987

The var iation of G with T is given by, G 0 = - RT lnK


-7.3745

7.01x10 3
0.045 x10 6 2 9153.26
G 0 = -2T
ln T
T
T
11.7987
2x 2
6x2
2T
2

3
6
-7.3745

7.01x10
0.045 x10
9153.26
0
G1500
= -2x1500
ln1500
1500
1500 2
11.7987
2x 2
6x2
2x1500
2

0
G1500

Pr oducts

G 28488.81

Re ac tan ts

g Cal
g mol

The reaction is not feasible G is highly +ve: For feasibility it should equal to zero

The hydration of Ethylene to alcohol is given by


Temperature 0C

145

6.8 x 10-2

Equilibrium Constant

320

1.9 x 10-3

C2H2 + H2O C2H5OH

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Component a

bx103

C2H4

2.83

28.601

The heat capacity data for the component can be

H2O

7.3

2.46

represented by Cp = a + bT where T is in kelvin

C2H5OH

6.99

39.741

and Cp is in cal / g mol 0C

Develop general expression for the equilibrium constant and standard Gibbs free
energy change as function of temperature.
a

Pr oducts

Pr oducts

lnK =

a = 6.99 (2.83 7.3) 3.14

Re ac tan ts

b 39.741x10 3 (28.6 x10 3 2.46 x10 3 ) 8.68 x10 3

Re ac tan ts

a
b
c 2
I
ln T
T
T
M
R
2R
6R
RT

3.14
8.68 x10 3
I
ln T
T
M
2
2x 2
2T

3.14
8.68 x10 3
I
At 418 K, ln 6.8x10 -2 =
ln 418
418
M
2
2x 2
2 x 418

Solving, I = -9655.807 & M = -5.667

3
3.14
8.68 x10
I
At 593 K, ln 1.9x10 -3
ln 593
593
M

2
2x 2
2 x 593

lnK =

3.14
8.68 x10 3
-9655.807
ln T
T
-5.667
2
2x 2
2T
3.14

8.68 x10 3
-9655.807
But G = -2T
ln T
T
-5.667
2
2
x
2
2
T

lnK =

G = 3.14T ln T - 4.34x10 -3T 2 9655.807 11.334T

THERMODYNAMIC FEASIBILITY OF REACTIONS


The equilibrium constant K is a measure of the concentration of the products
formed at equilibrium. It is related by the equation G 0 = - RT ln K. The more the value
of K, more will be the equilibrium conversion of products. When the value of G < 0,
means the value of K should be very large. Hence G is the measure of feasibility of a
chemical reaction.

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If G0 < 0, there can be appreciable conversion of reactants in to products.

i)

The more the ve value, more will be the feasibility of the reaction
If G0 is +ve but less than 10 000 k Cal / mol, the reaction is not feasible,

ii)

at atmosphere , may be feasible at any other pressure


If G0 is greater than 10 000 kCal / mol the reaction is not at all feasible

iii)

under any condition.


Equilibrium Calculations ( Homogeneous gas Phase reactions):
aA (g) + bB (g) cC (g) + dD (g)
ac ad
We have K Ca Db
a a
A B

for gases,

f
E as f 0 = p = 1 atmosphere: a = f
f0
but ac fc x p = c y c c p

Activity a
fc = c y c c

aD D yDD p
a A A y A A p
aB B yB B p

c yc c p D yDD p
a
b
A y A A p B yBB p
c

K=

c D

a
b
A B
c

y c yD
a
b
y A yB
c

c D
a
b
A B
c

p p
a
b
p p
c

K (k )(k y )( k )(Pc + d - (a + b) ) =( k )( k y )( k )(P n ) where = activity co efficient for gas phase


y = mole fraction

= Fugacity Co efficient for gas phase


P = Total pressure

Effect of variables on equilibrium :


0
RT ln K298 since G depends only on temperature as the
Effect of temperature: G298

pressure is fixed at 1.0 atmosphere, K value varies with temperature. It is not affected by
Pressure,
d ln K
dT

Concentration,
H
RT 2

etc,.

Variation

of

with

is

given

by

Van't Hoff equation.

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For endothermic reactions H0 is + ve as T increases K also increases. This


means that the equilibrium conversion is more at higher pressure.
For exothermic reactions H0 is ve. Therefore K increases with T. Hence the
equilibrium conversion decreases as T increases. Eg. SO 2 + 1/2 O2 SO3
Effect of pressure: Consider a reaction of ideal gases, then K = KyPn or Ky = K / Pn

When n > 0. An increase in pressure decreases Ky. Hence equilibrium product


yield is less at high pressures

When n< 0.

An increase in pressure increases Ky and equilibrium product

yield
C2H4 + H2O C2H5OH
N2 + 3H2 2NH3

n = 1 (1+1) = -1, n < 0


n = 2 4 = 2

n < 0 Here high

pressure is required

When n = 0 Here pressure has no effect on reaction. For ideal gases the effect
of pressure depends on the variation of and with pressure

Effect of Inert: Presence of inert has the opposite effect of increase of pressure.
Therefore when n

> 0, addition of inert increases Ky and equilibrium

conversion
And n < 0, addition of inert decreases equilibrium conversion.
Effect of excess reactants: Presence of excess reactants increases equilibrium
conversion of the limiting reactant
Presence of products in feed: decreases the equilibrium conversion of reactants.
Eg. CH3COOH + C2H5OH CH3COOC2H5 + H2O
If water is added by 1.0 mole to the feed, equilibrium conversion of CH 3COOH
reduces from 30% to 15%
HCN is produced by the reaction N2 (g)+ C2H2 (g) 2HCN (g). The reactants are
taken in stoichiometric ratio at 1.0 atmosphere and 3000C. At this temperature G0 = 30100

k J / k mol. Calculate equilibrium composition of product stream

and

maximum conversion of C2H2

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n=2 (1+1) = 0

we have G0 RT ln K or lnK =

or K = 1.8029x103

Moles

Moles

Moles

Mole

in feed

reacted

present

fraction

N2

1X

(1 X) / 2

C2H2

1X

(1 X) / 2

HCN

--

2X

2X

Component

K K K y K P n

30100
8.314(573)

(2X) / X =
X

Assume K K 1 and P n P 0 1

K 1.8029(10)3 K y

2
y HCN

y N1 2 yC1 2H2

X2
1 X 1 X
2 2

Solving for X , X = 0.0207

Equilibrium Composition:
1 X
1 0.0207
N2
100

100 48.965%
2
2

1 X
1 0.0207
C2 H2
100

100 48.965%
2
2

HCN ( X )100 2.007%


Equilibrium Conversion of C2 H 2
Equilibrium conversion is max imum for reversible reaction
Moles of C2 H2 reacted
X
0.0207
Max. Conversion of C2 H2
100 100
100 2.07%
Moles of C2 H2 in feed
1
1

Workout the problem, when the pressure is changed to 203 bar. Fugacity co efficients
of N2,,C2H2 and HCN are 1.1, 0.928, and 0.54 Assume K= 1
c
K K K y K P n = (1) a C b
A B

y Cc
a b
yA yB

0
203 where a,b, and c are stoichiometric co efficients

0.542
X2
and K is known already = 1.8029x10 -3 =
.(1)

(1.1)(0928) 1-X 1-X


2 2

solving X = 0.0382
then equilibrium Composion of C2H2 is ( Max reversible reaction)
moles C2 H2 reacted
0.0382
=
x 100 = 3.82%
moles of C2 H2 in feed
1

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Calculate the K at 673K & 1.0 bar for N2 (g) + 3 H2 (g) 2NH3 (g).
Assume heat of reaction remains constant. Take standard heat of formation and
standard free energy of formation of NH3 at 298 K to be - 46110 J / mol and 16450 J
/ mol respectively.
0
G298
2( 16450) 32900 J

0
H298 2 (-46110) = -92 220 J

0
G298
RT ln K 298
0
G298
RT ln K1

- 32900 = - 8.314 (298) ln K1


K1 564861.1
K2
H 1
1


K1
R T2 T1
K2
92220 1
1
ln

584861.1
8.314 673 298
0

we have ln

K 2 5.75 X 10 4

Acetic acid is esterified in the liquid phase with ethanol at 373 K and 1.0 bar according
to
CH3COOH (L) + C2H5OH (L) CH3COOC2H5(L) + H2O (L)
The feed consists of 1.0 mol each of acetic acid & ethanol, estimate the mole fraction of
ethyl acetate in the reacting mixture at equilibrium. The standard heat of formation
and standard free energy of formation at 298 K are given below.

Assume that the heat of reaction is independent of T and liquid mixture behaves as
ideal solution.

f0f
(J)
G0f
(J)

CH3COOH

C2H5OH

(L)

(L)

- 484500

- 277690

- 463250

- 285830

- 389900

-174780

- 318218

- 237130

CH3COOC2H5(L) H2O (L)

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G0298 = 318218 237130 + 389900 + 174780 = 9332 J


H0298 = 463250 285830 + 277690 + 484500 = 13110 J
We have, G0298 = RT ln K
9332 = 8.314 (298) ln K1

or K1 = 0.02313
K1
H 1
1


K2
R T1 T2
0.02313
12110 1
1
ln

K2
8.314 298 373
ln

and for K2 at 373K we have

OR K 2 0.067

Moles

Moles

Moles

Mole

in feed

reacted

present

fraction

CH3COOH

1X

(1 X) / 2

C2H5OH

1X

(1 X) / 2

CH3COOC2H5 --

X/2

H2O

X/2

Component

--

K2 K y P 0

0.067=

x
2

1 x
2

mole fraction of CH3 COOC2 H5

x2
(1 x )2

solving, x = 0.252

x 0.252

0.126
2
2

The standard free energy change for the reaction C4H8 (g) C4H6 (g) + H2 (g)
is given by GT0 =1.03665 X 105 20.9759T ln T 12.9372 T, where range of GT0 in J
/ mol and T in K
a) Over what range of T, is the reaction promising from thermodynamic view
point?
b) For a reaction of pure butene at 800K, calculate equilibrium conversion at 1.0
bar & 5.0 bar
c) Repeat part (b) for the feed with the 50 mol% butene and the rest inerts

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For the reaction at G = 0, T 812.4 K, above this temperature G <

a.

0, reaction is promising below 550 K, G > 0, reaction is unfavorable,


At 800K, G0 = 1842.16 J / mol

b.

G0 = - RT ln K,

or

1842.16 = - 8.314 ( 800 ) ln K

or

K = 1.3191
K = ky Pn = ky P ( 2- 1 ) = ky P

Therefore

at 1.0 bar K = kyP

ky = 1.31910At 5 bar,

1.3191 = ky ( 1 )
1.3191 = ky ( 5 )

ky = 0.26382

Moles

in Moles in product stream

feed
C4H8

yi
(1 X ) / (1 +

1-X

X)

C4H6

X / (1 + X)

H2

X / (1 + X)

1+X

kY

'
C4 H 6

'
H2

YC' 4H8

x x

1 x 1 x

1 x

1 x

or 1.3191 =

x2
or
1 x2

x = 0.7541

Conversion of betene = 75.41%


At 5.0 bar, k y = 0.26382 =

x2
,
1 x2

x = 0.4569, Conversion of betene = 45.69 %

C.
Moles

in Moles in product stream

feed
C4H8
C4H6

yi

1-X

(1 X ) / (2 + X)

X / (2 + X)

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H2
Inerts

1.0

X / (2 + X)

1 / (2 + X)

2+x

at 1.0 bar,

k Y K 1.3191

x2

2 x

2x

1 x

x = 0.8194
at 5.0 bar

kY

K
x2 2 x
0.26382

2
5
2 x 1 x

x = 0.5501

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